KR20160147832A - Hydrogenated block copolymer composition and adhesive composition - Google Patents

Abstract

(A) having a weight average molecular weight of 30,000 or more and 500,000 or less and a polymer block containing at least one polymer block mainly composed of at least one vinyl aromatic hydrocarbon and at least one polymer block having a conjugated diene compound as a main component, (B) containing a polymer block composed mainly of an aromatic hydrocarbon and a polymer block composed mainly of at least one conjugated diene compound and having a weight average molecular weight of 50,000 or more and 1,000,000 or less and satisfying a predetermined requirement Hydrogenated block copolymer composition.

Description

HYDROGENATED BLOCK COPOLYMER COMPOSITION AND ADHESIVE COMPOSITION [0001] The present invention relates to a hydrogenated block copolymer composition,

The present invention relates to a hydrogenated block copolymer composition and a point-stick adhesive composition using the same.

In recent years, hot-melt type point adhesives have been widely used from the viewpoints of energy saving, resource saving, environmental load reduction, and the like, and as a base polymer of hot melt type point adhesive, a vinyl aromatic monomer-conjugated diene monomer block copolymer (For example, SBS: styrene-butadiene-styrene-block copolymer) have been widely used. However, with respect to the pressure-sensitive adhesive compositions obtained by using these block copolymers, the balance between retention force, tack and adhesive force is insufficient, and improvement thereof has been desired.

As an improvement method thereof, for example, Patent Document 1 discloses a tacky adhesive composition comprising a triblock copolymer and a diblock copolymer. Patent Document 2 discloses a point-adhesive composition comprising a block copolymer obtained by coupling with a specific bifunctional coupling agent (specific dihalogen compound). Patent Document 3 discloses a pressure-sensitive adhesive composition comprising a block copolymer in which a block copolymer of a vinyl aromatic monomer and a conjugated diene monomer is hydrogenated at a specific ratio (hereinafter, simply referred to as "hydrogenation").

Japanese Patent Application Laid-Open No. 61-278578 Japanese Patent Application Laid-Open No. 63-248817 Japanese Patent Application Laid-Open No. 05-98130

However, even in the above-mentioned conventionally proposed technique, it is not always possible to sufficiently improve the balance of the holding force, the tack, and the adhesive force, and in particular, a further improvement in the tack is desired. In addition, the balance between these point-sticking properties and the feel of the point adhesive (irregularity followability) is insufficient.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a pressure-sensitive adhesive composition which has excellent adhesive properties such as retention, tack and adhesive strength, To provide a hydrogenated block copolymer composition capable of exhibiting excellent physical properties in terms of feeling and balance thereof, and a point adhesive composition comprising the hydrogenated block copolymer composition.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the problems of the prior art, and as a result, they have found that a hydrogenated block copolymer composition having a specific structure can solve the problems of the prior art described above, It has been found that the above-mentioned problems of the prior art can be solved also in a point-adhesive composition containing a composition and a tackifier in predetermined amounts, respectively, and the present invention has been completed.

That is, the present invention is as follows.

[One]

(A) containing a polymer block composed mainly of at least one vinyl aromatic hydrocarbon and a polymer block composed mainly of at least one conjugated diene compound and having a weight average molecular weight of 30,000 or more and 500,000 or less,

(B) containing a polymer block composed mainly of at least two vinyl aromatic hydrocarbons and a polymer block composed mainly of at least one conjugated diene compound and having a weight average molecular weight of 50,000 or more and 1,000,000 or less,

Lt; / RTI >

A hydrogenated block copolymer composition which satisfies the following requirements (a) to (c):

(a) the total hydrogenation ratio H (%) of the unsaturated double bond based on the conjugated diene compound is 5 to 90%

(b) the maximum value of the loss coefficient tan? at -100 DEG C to 0 DEG C is 0.4 to 4.0

(c) a ratio of the weight average molecular weight of the component (A) to the component (B)

(Weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3 to 10.

[2]

The hydrogenated block copolymer composition according to [1], wherein the component (A) is 20 mass% or more and 90 mass% or less, and the component (B) is 10 mass% or more and 80 mass% or less.

[3]

The hydrogenated block copolymer composition according to [1] or [2], wherein the SP value is 17.2 (MPa) ^1/2 or more and 17.7 (MPa) ^1/2 or less.

[4]

The conjugated diene compound polymer block is an SP value of 16.8 to a subject (㎫) more than ^1/2, 17.5 (㎫) ^1/2 or less, of [1] to [3] of the hydrogenated block copolymer composition according to any one .

[5]

The hydrogenated block copolymer composition according to any one of [1] to [4], wherein the component (B) has a weight average molecular weight of 140,000 or more and 600,000 or less.

[6]

The hydrogenated block according to any one of [1] to [5], wherein the component (B) contains a polymer block composed mainly of two vinyl aromatic hydrocarbons and a polymer block composed mainly of at least one conjugated diene compound Copolymer composition.

[7]

The hydrogenated block copolymer composition according to any one of [1] to [6], wherein the component (B) has a weight average molecular weight of 200,000 or more and 600,000 or less.

[8]

The hydrogenated block copolymer composition according to any one of [1] to [7], wherein the conjugated diene compound is butadiene.

[9]

The hydrogenated block copolymer composition according to any one of [1] to [8], wherein the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is 5 mass% or more and less than 35 mass%.

[10]

The hydrogenated block copolymer composition according to any one of claims 1 to 9, wherein the content of the vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer composition is 5 mass% or more and less than 20 mass%.

[11]

The hydrogenated block copolymer composition according to any one of [1] to [10], wherein the maximum value of the loss coefficient tan? Is 0.7 to 1.6.

[12]

The hydrogenated block copolymer composition according to any one of [1] to [11], wherein the maximum value of the loss coefficient tan? Is 0.9 to 1.6.

[13]

The hydrogenated block copolymer composition according to any one of [1] to [12], wherein the temperature at which the maximum value of the loss coefficient tan? Is taken is -75 占 폚 or higher and -50 占 폚 or lower.

[14]

The hydrogenated block copolymer composition according to any one of [1] to [13], wherein the component (A) has a weight average molecular weight of 70,000 or more and 300,000 or less.

[15]

A pressure-sensitive adhesive composition comprising the hydrogenated block copolymer composition according to any one of [1] to [14]

With respect to 100 parts by mass in total of the polymer contained in the point adhesive composition,

20 to 500 parts by mass of the tackifier,

0 to 300 parts by mass of a softener

Wherein the pressure-sensitive adhesive composition further comprises a pressure-sensitive adhesive.

[16]

The pressure-sensitive adhesive composition according to [15], further comprising a vinyl aromatic elastomer.

[17]

Wherein the vinyl aromatic elastomer contains a polymer block composed mainly of at least one vinyl aromatic hydrocarbon and a polymer block composed mainly of at least one conjugated diene compound and having a loss coefficient tan? , The maximum value is less than 0.4, and the hydrogenation ratio H (%) of the unsaturated double bond based on the conjugated diene compound is 5 to 90%.

[18]

The pressure-sensitive adhesive composition according to any one of [15] to [17], further comprising a conjugated diene-based synthetic rubber.

[19]

The point-adhesive composition according to any one of claims 15 to 18, further comprising a natural rubber.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive composition which has excellent retention, tack and adhesive strength, particularly excellent tack, It is possible to provide a pressure-sensitive adhesive composition comprising the block copolymer composition and the hydrogenated block copolymer composition.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as " present embodiment ") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention. In the following, the structural unit constituting the polymer is referred to as a " monomer unit ", and when describing it as a polymer material, " unit " is omitted and is simply described as " monomer.

[Hydrogenated block copolymer composition]

The hydrogenated block copolymer composition of the present embodiment comprises a polymer block composed mainly of at least one vinyl aromatic hydrocarbon (hereinafter also simply referred to as "polymer block Ar") and a polymer block composed mainly of at least one conjugated diene compound (Polymer block Ar) containing at least two vinyl aromatic hydrocarbons and a component (A) having a weight average molecular weight of 30,000 or more and 500,000 or less and a polymer block And a component (B) containing a polymer block (polymer block D) containing at least one conjugated diene compound as a main component and having a weight average molecular weight of 50,000 or more and 1,000,000 or less. Further, the hydrogenated block copolymer composition of the present embodiment satisfies the following requirements (a) to (c):

(a) the total hydrogenation ratio H (%) of the unsaturated double bond based on the conjugated diene compound is 5 to 90%

(b) the maximum value of the loss coefficient tan? at -100 DEG C to 0 DEG C is 0.4 to 4.0

(c) a ratio of the weight average molecular weight of the component (A) to the component (B)

(Weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3 to 10.

Since the hydrogenated block copolymer composition of the present embodiment has the above-described constitution, it has an excellent holding power, a tack and an adhesive force, and is excellent in a point-stick property, a low melt point property, An excellent balance of physical properties can be exhibited.

In the present embodiment, when a plurality of polymer blocks Ar and / or D is present in the block copolymer of the component (A) and / or the component (B), the weight average molecular weight of each of the polymer blocks Ar and D, , The structures may be the same or different.

Means that the content of the vinyl aromatic hydrocarbon monomer unit in the polymer block is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more , And more preferably 95 mass% or more.

Means that the content of the conjugated diene compound monomer unit in the polymer block is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, Or more, and more preferably 95 mass% or more.

The content of the component (A) and the component (B) in the hydrogenated block copolymer composition is preferably 20% by mass or more and 90% by mass or less and the component (B) is 10% by mass or more and 80% Or less. When the content of the component (A) and the component (B) is within the above range, the tendency of obtaining a hydrogenated block copolymer composition and a pressure-sensitive adhesive composition having both a low melt viscosity and a good point- . From the same viewpoint, it is more preferable that the component (A) is 30 mass% or more and 80 mass% or less and the component (B) is 20 mass% or more and 70 mass% By mass or more and 75% by mass or less, and the component (B) is 25% by mass or more and 65% by mass or less. More preferably, the component (A) is 40 mass% or more and 70 mass% or less, and the component (B) is 30 mass% or more and 60 mass% or less.

The hydrogenated block copolymer composition of the present embodiment may contain a polymer other than the component (A) and the component (B), and the content of the polymer other than the component (A) and the component (B) is preferably 50% More preferably 30% by mass or less, further preferably 20% by mass or less, even more preferably 10% by mass or less, particularly preferably 0% by mass.

The content of the component (A) and the component (B) can be controlled within the above-mentioned range by adjusting various conditions of the production method described later. The content of the component (A) and the component (B) can be measured by the method described in the following examples.

The maximum value of the loss coefficient (tan?) At -100 DEG C to 0 DEG C in the dynamic viscoelastic spectrum of the hydrogenated block copolymer composition containing the component (A) and the component (B) is 0.4 to 4.0. When the maximum value of the loss coefficient is 0.4 or more, a hydrogenated block copolymer composition and a viscous composition having excellent feel and tack are obtained. A hydrogenated block copolymer composition and a viscous composition having excellent holding power are obtained when the viscosity index is 4.0 or less. From the same viewpoint, it is preferably 0.5 or more, more preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and still more preferably 0.9 or more. It is preferably 2 or less, more preferably 1.8 or less, and even more preferably 1.6 or less. Since the maximum value of the loss coefficient (tan?) Is 0.7 to 1.6, particularly excellent tactile feel is obtained, and 0.9 to 1.6 is particularly excellent.

The hydrogenated block copolymer composition and the viscous adhesive composition excellent in touchability are excellent in the irregularity followability of an adherend.

The temperature at which the maximum value of the loss coefficient (tan?) At -100 deg. C to 0 deg. C is given is preferably -75 deg. C to -50 deg. When the temperature at which the maximum value of the loss coefficient (tan delta) is given is within this range, the low-temperature characteristics are good and the degree of freedom in compounding increases.

In order to control the tan delta of the hydrogenated block copolymer composition to the above-mentioned range, the content of the vinyl aromatic hydrocarbon monomer unit and the hydrogenation rate in the component (A) and the component (B) By controlling the structure of the hydrogenated block copolymer or the conditions for preparing the hydrogenated block copolymer composition.

In order to increase the maximum value of the value of tan delta, it is not limited to the following. For example, it is preferable to increase the amount of the monomer added at the time of the polymerization reaction, to decrease the difference between the maximum value and the minimum value of the temperature of the solution at the time of polymerization , The difference between the maximum value and the minimum value of the temperature of the solution at the time of the hydrogenation reaction is made small, and the ratio of the height (H) and the inside diameter (diameter) of the reactor used for the hydrogenation reaction is increased The same can be said. Specifically, in order to set the maximum value of tan? To 0.4 or more, the number of monomer addition sites at the time of polymerization is preferably 2 or more, more preferably 3 or more, and the maximum value and the minimum value Is preferably 15 DEG C or lower, more preferably 5 DEG C or lower, and the difference between the maximum value and the minimum value of the temperature of the solution in the hydrogenation reaction is preferably 19 DEG C or lower, more preferably 5 DEG C or lower, The ratio of the height (H) to the inner diameter (diameter, D) of the reactor used in the reaction is preferably 5 or more.

In order to reduce the maximum value of the value of tan delta, it is not limited to the following. For example, it is preferable to decrease the amount of the monomer added at the time of the polymerization reaction, to increase the difference between the maximum value and the minimum value of the temperature of the solution during the polymerization reaction , The difference between the maximum value and the minimum value of the temperature of the solution at the time of the hydrogenation reaction is increased, the ratio of the height H and the inside diameter (diameter) of the reactor used for the hydrogenation reaction is decreased . Specifically, in order to set the maximum value of tan? To 4.0 or less, the number of monomer addition sites in the polymerization reaction is preferably 5 or less, and the difference between the maximum value and the minimum value of the temperature of the solution during the polymerization reaction is preferably 0.1 DEG C or more , The difference between the maximum value and the minimum value of the temperature of the solution at the time of the hydrogenation reaction is preferably 0.1 DEG C or more and the ratio of the height H to the inside diameter (diameter) of the reactor used for the hydrogenation reaction is preferably 7 or less Do.

In addition, when butadiene is used as the conjugated diene compound monomer, the maximum value of tan? Tends to be 2.0 or less. Also, as the content of the vinyl aromatic hydrocarbon monomer unit becomes smaller, the value of tan? Tends to increase. Concretely, when the content of the vinyl aromatic hydrocarbon monomer unit is less than 20% by mass, the maximum value of tan? Tends to take a value of 0.6 or more although it depends on the conditions at the time of production.

In the dynamic viscoelastic spectrum obtained with respect to the hydrogenated block copolymer composition, the peak of the loss coefficient existing in the above range is a peak due to the polymer block (D) containing a conjugated diene compound as a main component. Outside of the above range, a peak of loss coefficient may or may not exist.

The dynamic viscoelastic spectrum can be controlled within the above range by adjusting various conditions of the manufacturing method as described above. Further, the spectrum of the dynamic viscoelasticity can be measured by the method described in Examples to be described later.

The ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) (weight average molecular weight of the component (B)) / (weight average molecular weight of the component (A)) is 1.3 or more and 10 or less. When the ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) is within the above-mentioned range, the hydrogenated block copolymer composition having excellent low-melt viscosity characteristics, Thereby obtaining a pressure-sensitive adhesive composition. From the same viewpoint, it is preferably 1.5 or more and 8.0 or less, and more preferably 1.8 or more and 5.0 or less. The ratio of the content of the component (A) and the component (B), the weight average molecular weight and the weight average molecular weight can be controlled within the above range by adjusting various conditions of the production method described later. The ratio of the content of the component (A) and the component (B), the weight average molecular weight and the weight average molecular weight can be measured by the method described in the following examples. Hereinafter, each component will be described in more detail.

[Block Copolymer]

(Component (A))

The component (A) is a polymer block (D) composed mainly of a polymer block (Ar) containing at least one vinyl aromatic hydrocarbon (vinyl aromatic hydrocarbon monomer unit) and at least one conjugated diene compound (conjugated diene compound monomer unit) ≪ / RTI > or mixtures thereof. The weight average molecular weight of the block copolymer of the component (A) is 30,000 or more and 500,000 or less. A hydrogenated block copolymer composition having excellent low-melt-viscosity characteristics and feel by having the weight-average molecular weight of the component (A) of 30,000 or more and excellent in productivity and having a weight average molecular weight of 500,000 or less, A point-adhesive composition is obtained. From the same viewpoint, it is preferably at least 50,000, more preferably at least 70,000. Further, it is preferably 175,000 or less, and more preferably 150,000 or less. The weight average molecular weight of the component (A) can be determined by the method described in the examples.

The structure of the component (A) is not particularly limited, and examples thereof include the following formulas (i) to (vi).

In the formulas (i) to (vi), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon, D represents a polymer block (D) mainly comprising a conjugated diene compound, And m, n and k represent an integer of 1 or more and preferably an integer of 1 to 6, Ar may be the same or different in kind and molecular weight of the vinyl aromatic hydrocarbon monomer in the case where a plurality is present, and D in the case where a plurality of vinyl aromatic hydrocarbon monomers are present may be the same or different in kind and molecular weight of the conjugated diene compound monomer.

Among the above formulas (i) to (vi), a block copolymer having one Ar is preferable, and a block copolymer represented by Ar-D and D-Ar-D is more preferable. When the component (A) has such a structure, there is a tendency that a hydrogenated block copolymer composition and a pressure-sensitive adhesive composition having better low-melt viscosity characteristics, adhesive strength, tack and feeling, and better balance are obtained.

(Component (B))

The component (B) is a polymer block (D) composed mainly of a polymer block (Ar) composed mainly of at least two vinyl aromatic hydrocarbons (vinyl aromatic hydrocarbon monomer units) and at least one conjugated diene compound (conjugated diene compound monomer units) ≪ / RTI > or mixtures thereof. The weight average molecular weight of the block copolymer of the component (B) is 50,000 or more and 1,000,000 or less. When the weight average molecular weight of the component (B) is 50,000 or more, the component (B) has a weight-average molecular weight of 1,000,000 or less, thereby providing a hydrogenated block copolymer having excellent low- A composition and a pressure-sensitive adhesive composition are obtained. From the same viewpoint, it is more preferably 100,000 or more, more preferably 140,000 or more, still more preferably 200,000 or more. It is more preferably 500,000 or less, still more preferably 300,000 or less. The weight average molecular weight of the component (B) can be determined by the method described in the Examples.

The structure of the component (B) is not particularly limited, and examples thereof include the following formulas (vii) to (xii).

In the formulas (vii) to (xiii), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon, D represents a polymer block (D) mainly comprising a conjugated diene compound, E and f represent an integer of 2 or more, g represents an integer of 1 or more, and is preferably a positive integer of 6 or less. When a plurality is present, Ar may be the same or different from each other in the kind and molecular weight of the vinyl aromatic monomer, and in the case where a plurality is present, the kind and molecular weight of the conjugated diene monomer may be the same or different.

Among the above-mentioned formulas (vii) to (xiii), the component (B) is a block copolymer having two Ar's in that a balance of productivity and adhesive property is good, g is preferably 1 in formula (xi) or formula (xii), more preferably 3 or 4 in formula (xi) or g = 1 in formula (xii) _{Ar, (Ar-D) 2} X, D-Ar-D-Ar, D-Ar-D-Ar-D, D- (Ar-D) 2 X, [D- (Ar-D) 1] 3 - X, [(Ar-D) 1] 3 -X, [D- (Ar-D) 1] 4 -X and / or [(Ar-D) _1] comprising a block copolymer represented by -X ₄ Is more preferable. When the component (B) contains such a block copolymer, there is a tendency to obtain a hydrogenated block copolymer composition and a pressure-sensitive adhesive composition which are more excellent in productivity and viscosity.

(B) is preferably a hydrogenated block copolymer composition containing a polymer block composed mainly of two vinyl aromatic hydrocarbons and a polymer block composed mainly of at least one conjugated diene compound . The block copolymer of the above-mentioned component (B) preferably has a weight average molecular weight of 140,000 or more. The hydrogenated block copolymer composition containing a polymer block composed mainly of two vinyl aromatic hydrocarbons and a polymer block composed mainly of at least one conjugated diene compound is not particularly limited and examples thereof include a compound represented by the formula Ar-D-Ar , there may be mentioned _{(Ar-D) 2 X,} D-Ar-D-Ar, D-Ar-D-Ar-D, D- (Ar-D) 2 X , and mixtures thereof and the like.

The content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition of the present embodiment is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. The content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is preferably less than 35% by mass, more preferably less than 30% by mass, further preferably less than 20% by mass. When the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition of the present embodiment is within the above range, the tendency of obtaining a hydrogenated block copolymer composition and a point adhesive composition having excellent point bonding performance and excellent balance thereof . Particularly, when the content of the vinyl aromatic hydrocarbon monomer unit is 5 mass% or more, there is a tendency to obtain a hydrogenated block copolymer composition and a pressure-sensitive adhesive composition having excellent adhesive force and holding power. Further, when the content of the vinyl aromatic hydrocarbon monomer unit is less than 35% by mass, there is a tendency that a hydrogenated block copolymer composition and a point-adhesive composition having excellent tackiness are obtained. The content of the vinyl aromatic hydrocarbon monomer unit is particularly preferably at least 5 mass% and less than 20 mass%.

Here, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is not a value per component but an average value of the content of the hydrogenated block copolymer composition as a whole, that is, the content of each component. The content of the vinyl aromatic monomer unit in the hydrogenated block copolymer composition can be measured by the method described in the following Examples.

In addition, the vinyl bond amount of the conjugated diene compound monomer unit in the hydrogenated block copolymer composition of the present embodiment is preferably less than 80 mol%, more preferably less than 70 mol%, still more preferably less than 50 mol%. The vinyl bond amount of the conjugated diene compound monomer unit is preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, still more preferably 25 mol% or more, Is at least 30 mol%. More specifically, the vinyl bond amount of the conjugated diene compound monomer unit in the component (A) and the component (B) is preferably from 5 mol% to less than 80 mol%, more preferably from 8 mol% to less than 70 mol% , Preferably not less than 10 mol% and less than 50 mol%. When the vinyl bond amount of the conjugated diene compound monomer unit is within the above range, excellent characteristics are obtained due to productivity, tack, and adhesion.

Here, the amount of vinyl bond of the conjugated diene compound monomer unit is not a value per component, but the amount of the vinyl bond as a whole of the block copolymer composition, that is, the total molar amount of all the conjugated diene compound monomer units contained in the composition (The conjugated diene compound monomer unit incorporated in the polymer in the 1,2-bond bonding mode) and the total 3,4-vinyl bond amount (the bonding form of the 3,4-bond (Unit of the conjugated diene compound monomer unit incorporated into the polymer).

The amount of vinyl bonding of the hydrogenated block copolymer composition means the amount of the conjugated diene compound incorporated in the polymer in the bonding mode of 1,2-bond, 3,4-bond and 1,4-bond at the time before hydrogenation Is the ratio of the total molar amount of the conjugated diene compound monomer units incorporated in the 1,2-bond and the 3,4-bond at the time before hydrogenation with respect to the total molar amount of the monomer units.

Further, after hydrogenation, a hydrogen-free 1,2-bond, a 1,2-bond after hydrogenation, a 3,4-bond without hydrogen addition, a 3,4-bond after hydrogenation, , The total molar amount of the conjugated diene compound monomer units assembled in the bonding mode of the 4-bond and the 1,4-bond after the hydrogenation, 1,2-bond after hydrogen addition, 1,2-bond after hydrogenation , The ratio of the total molar amount of the conjugated diene compound monomer units incorporated in the 3,4-bond not added with hydrogen and the 3,4-bond after hydrogenation is equivalent to the amount of vinyl bond in the conjugated diene monomer unit. That is, the amount of vinyl bonding does not change before and after hydrogenation. Therefore, the vinyl bonding amount of the conjugated diene compound monomer unit can be measured by nuclear magnetic resonance spectrum analysis (NMR) using a block copolymer composition before or after hydrogenation, and specifically, the method described in Examples .

The values of the contents of the vinyl aromatic hydrocarbon monomer units, the weight average molecular weights of the component (A) and the component (B), and the contents of the component (A) and the component (B) are substantially the same before and after the hydrogenation, Value.

In the hydrogenation step, the conjugated bond of the vinyl aromatic hydrocarbon monomer unit may be hydrogenated, but the hydrogenation ratio of the conjugated bond of the entire vinyl aromatic hydrocarbon monomer unit is preferably 30 mol% or less, more preferably 10 mol% or less, Or less, more preferably 3 mol% or less.

The total hydrogenation ratio H of unsaturated double bonds based on the conjugated diene compound in the hydrogenated block copolymer composition of the present embodiment is 5 mol% or more and 90 mol% or less. When the total hydrogenation ratio H is within the above range, a hydrogenated block copolymer composition and a pressure-sensitive adhesive composition each having excellent viscous property, low melt viscosity, excellent touch, and excellent balance can be obtained. From the same viewpoint, it is preferably not less than 15 mol%, more preferably not less than 20 mol%, and still more preferably not less than 25 mol%. With such a hydrogenation rate, retention, tack, and adhesion tend to be more excellent. The total hydrogenation ratio H is preferably less than 80 mol%, more preferably 70 mol% or less, still more preferably 60 mol% or less. With such a hydrogenation rate, there is a tendency that the low viscosity property and the feeling are superior. From the same viewpoint as the above, the total hydrogenation ratio H is preferably 15 mol% or more and less than 80 mol%, more preferably 20 mol% or more and less than 70 mol%, and still more preferably 25 mol% or more and less than 60 mol%. The total hydrogenation ratio H can be measured by the method described in the Examples.

In the present embodiment, the hydrogenation rate refers to the ratio of hydrogenated unsaturated double bonds to unsaturated double bonds based on the conjugated diene compound before hydrogenation. The total hydrogenation rate refers to the hydrogenation rate of the entire composition, that is, the ratio of hydrogenated unsaturated double bonds among the unsaturated double bonds based on all the conjugated diene compounds contained in the composition before hydrogen is added.

The hydrogenation ratio of each of the components (A) and (B) is preferably from 5 to 90 mol%, more preferably from 15 to 80 mol%, still more preferably from 20 to 70 mol% Is 25 to 60 mol%.

For the same reason, it is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less, More preferable.

Conjugated SP value of the polymer block to the diene compound as a main component in the hydrogenated block copolymer of this embodiment the composition is not less than 16.8 ((㎫) ^1/2) preferably, greater than 16.97 ((㎫) ^1/2) Is preferably 17.0 ((MPa) ^1/2 ) or more, more preferably 17.5 ((MPa) ^1/2 ) or less, and more preferably 17.2 or less. 16.8 to 17.5 ((MPa) ^1/2 ). It is more preferable that the polymer block having a conjugated diene compound as a main component has an SP value of 16.97 to 17.5 (MPa) ^1/2 , more preferably 17.0 to 17.2 (MPa) ^1/2 .

In addition, SP value of the hydrogenated block copolymer composition is 17.2 ((㎫) ^1/2) or less preferably, and preferably from 17.3 ((㎫) ^1/2) preferably 17.7 ((㎫) ^1/2) or greater , And is preferably 17.55 ((MPa) ^1/2 ) or less. Further, it is preferably 17.2 to 17.7 (MPa) ^1/2 , more preferably 17.2 to 17.55 (MPa) ^1/2 , and further preferably 17.3 to 17.55 (MPa) ^1/2 .

From the viewpoints of excellent point-bonding properties and / or low-melt viscosity characteristics and balance thereof, the polymer block having a conjugated diene compound as a main component in the hydrogenated block copolymer composition has an SP value of 16.97 to 17.5 ((MPa) ^1/2 ) And the SP value of the hydrogenated block copolymer composition is 16.2 to 17.7 ((MPa) ^1/2 ), and it is preferable that the SP value of the hydrogenated block copolymer composition is also satisfied simultaneously.

Here, the SP value of the hydrogenated block copolymer composition is an imaginary value, and a value obtained by using a calculation method described later is described as an SP value in the present specification.

By taking the SP value as described above, the hydrogenated block copolymer composition and the pressure-sensitive adhesive composition are excellent in the point-stick properties.

The SP value of the polymer block composed mainly of the conjugated diene compound is calculated from the formula (SP value) = ((moles of cohesive energy) / (molar volume)) ^1/2 . In the case where the polymer block composed mainly of the conjugated diene compound is composed of two or more different monomer components, moles of cohesive energy is pseudomorphic. From the content (mol%) of each component and the molar cohesive energy, The moles of cohesive energy of the block of the polymer mainly composed of the compound is calculated as an average value (average value calculated according to the content) of the moles of coagulation energy of each component. The molar volume of the block of the polymer having the conjugated diene compound as a main component, based on the content (mol%) and the molar volume of each component, is the same as the molar volume of each component (Average value calculated according to the content ratio).

The two or more different kinds of components are not particularly limited, and examples thereof include 1,2-bonds not added with hydrogen, 1,2-bonds after hydrogenation, 3,4-bonds not added with hydrogen, 3,4- A conjugated diene compound monomer unit and a vinyl aromatic hydrocarbon monomer unit which are assembled in a bonding mode of 1,4-bond not added with hydrogen and 1,4-bond after hydrogenation. Further, the respective amounts of the conjugated diene compound monomer units incorporated in each binding mode can be measured by NMR and the like.

Also, the SP value of the whole hydrogenated block copolymer composition can be determined by using the SP value of the polymer block constituting each component contained therein, Quot ;, Information < / RTI > (2007) p.56. The method for calculating the SP value of the copolymer was calculated to be applicable to block copolymers. (The SP value of the entire block copolymer composition) ² = (the SP value of Ar) ² x (the total volume fraction of Ar) + (the SP value of D) ² x ( The total volume fraction of D).

Further, the 1,2-bond not added with hydrogen, the 1,2-bond after hydrogenation, the 3,4-bond not added with hydrogen, the 3,4-bond after hydrogenation, the 1,4- The molar volume and moles of cohesive energy of conjugated diene monomer units, vinyl aromatic hydrocarbon monomer units, and other monomer units assembled in the 1,4-bond bonding mode after hydrogenation are described in J. Bicerano, Prediction of Polymer Properties, 3rd Ed. According to the method described by Marcel Dekker, 2002 (Bicerano method).

[Process for producing hydrogenated block copolymer composition]

The hydrogenated block copolymer composition is not limited to the following examples. For example, the hydrogenated block copolymer composition may be obtained by, for example, a polymerization step of polymerizing at least a conjugated diene compound monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent with an organolithium compound as a polymerization initiator, , A hydrogenation step of hydrogenating the double bond in the conjugated diene monomer unit, and a solvent removal step of removing the solvent of the solution containing the hydrogenated block copolymer in this order. Here, the component (A) and the component (B) may be separately prepared, mixed later, or simultaneously produced.

When the component (A) and the component (B) are produced at the same time, the ratio and the content of the weight average molecular weight and the weight average molecular weight of the component (A) and the component (B) Can be adjusted by controlling. The ratio and the content of the weight average molecular weight and the weight average molecular weight of the component (A) and the component (B) can be adjusted by controlling the addition amount and the number of addition of the polymerization initiator described later and dividing them by a plurality of circuits. The ratio of the weight-average molecular weight and the weight-average molecular weight of the component (A) to the component (B) can also be adjusted by controlling the addition amount of the defoaming agent to be described later and performing the deactivation step once and continuing the polymerization reaction .

(Polymerization step)

The polymerization process is not limited to the following process. For example, a process of polymerizing at least a monomer containing a conjugated diene compound monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent with an organic lithium compound as a polymerization initiator can be exemplified .

The polymerization reaction temperature is not particularly limited and is usually 10 to 150 占 폚, preferably 30 to 130 占 폚, and more preferably 40 占 폚 to 100 占 폚. The polymerization pressure may be in the range of the above polymerization temperature and in a range of a pressure sufficient to maintain the solvent and the liquid in the liquid phase, and is not particularly limited. The time required varies depending on conditions, and is not particularly limited, but is usually 48 hours or less, preferably 0.5 to 10 hours.

≪ Hydrocarbon solvent &

As described above, in the polymerization step, a hydrocarbon solvent can be used. Examples of the hydrocarbon solvent include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane and octane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane; And aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene. The hydrocarbon solvent may be used alone or in a mixture of two or more.

<Polymerization Initiator>

In the polymerization step, it is preferable to use at least an organic lithium compound as the polymerization initiator. The organic lithium compound is not particularly limited, and examples thereof include an organic monolithium compound in which at least one lithium atom is bonded to a molecule, an organic dirithium compound, and an organic polythiomide compound. More specifically, examples include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldithiol, have. The polymerization initiator may be used alone, or two or more thereof may be used in combination.

From the viewpoint of obtaining a composition containing a plurality of kinds of block copolymers having different weight average molecular weights or structures at once, it is preferable that the polymerization initiator is divided into a plurality of circuits and added to the reaction solution.

&Lt; Monomer used in polymerization >

The conjugated diene compound is a diolefin having a pair of conjugated double bonds. Examples of the conjugated diene compound monomer include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Diene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like. Of these, 1,3-butadiene and isoprene are preferred. From the viewpoint of improving the holding power of the viscous composition, 1,3-butadiene is more preferable. The conjugated diene compound monomer may be used alone, or two or more of them may be used in combination.

Examples of the vinyl aromatic hydrocarbon monomer include, but are not limited to, styrene,? -Methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N- N, N-diethyl-p-aminoethylstyrene, and the like. Of these, styrene is preferable from the viewpoint of economy. The vinyl aromatic hydrocarbon monomer may be used alone, or two or more kinds thereof may be used in combination.

The block copolymer contained in the component (A) and the component (B) may contain a vinyl aromatic hydrocarbon monomer unit and a monomer unit other than the conjugated diene compound monomer unit. In the polymerization process, the vinyl aromatic hydrocarbon monomer and the conjugated diene compound monomer Other monomers copolymerizable with the monomers may be used. Other monomers copolymerizable with the monomer are not particularly limited, and examples thereof include acrylonitrile, methyl alpha -cyanoacrylate, and methyl acrylate.

In the polymerization process, for the purpose of adjusting the polymerization rate, controlling the microstructure (cis, trans, vinyl ratio) of the polymerized conjugated diene compound monomer unit, and adjusting the reaction ratio of the conjugated diene compound monomer and the vinyl aromatic hydrocarbon monomer , A predetermined polar compound or a randomizing agent can be used.

Examples of the polar compounds and randomizing agents include, but are not limited to, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; Amines such as triethylamine and tetramethylethylenediamine; Thioethers, phosphines, phosphoramides, alkylbenzenesulfonates, alkoxides of potassium or sodium, and the like.

<Coupling agent>

(Iv) to (vi), in an amount such that the functional group is less than 1 molar equivalent with respect to the active terminal thereof, to the solution containing the vinyl aromatic hydrocarbon-conjugated diene compound block copolymer having active terminals, , a coupling agent represented by X in (x) to (xiii) may be added.

The coupling agent to be added is not particularly limited, but any coupling agent having two or more functionalities may be used. The bifunctional coupling agent is not particularly limited, and examples thereof include bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane and dimethyldichlorosilane; Bifunctional alkoxysilanes such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane; Bifunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride and dibromomethane; Bifunctional halogenated tin salts such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin and dibutyldichlorotin; Dibromobenzene, benzoic acid, CO, 2-chloropropene, and the like.

The trifunctional coupling agent is not particularly limited, and examples thereof include trifunctional halogenated alkanes such as trichloroethane and trichloropropane; Trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; Trifunctional alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; And the like.

The tetrafunctional coupling agent is not particularly limited, and examples thereof include tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide and tetrachloroethane; Tetrafunctional halogenated silanes such as tetrachlorosilane and tetrabromosilane; Tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; Tetrafunctional tin halides such as tetrachloro-tin and tetrabromo-tin; And the like.

The coupling agent having five or more functional groups is not particularly limited, and examples thereof include 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, decabromodi Phenyl ether, and the like. In addition, polyvinyl compounds such as epoxidized soybean oil, 2 to 6 functional epoxy group-containing compounds, carboxylic acid esters, and divinylbenzene may be used. The coupling agent may be used alone or in combination of two or more.

Above all, from the viewpoint of the color tone and low adverse effect on the plant, it is preferable that it is a non-halogen type coupling agent. From the viewpoint of productivity and low adverse effects on the plant, it is preferable that the compound is an epoxy group-containing compound or alkoxysilane.

As described above, when a coupling agent is added to a solution containing an aromatic vinyl hydrocarbon-conjugated diene compound block copolymer having an active terminal in an amount such that the functional group is less than 1 molar equivalent with respect to its active terminal, In some of the block copolymers of the aromatic vinyl hydrocarbon-conjugated diene compound block copolymer, the active terminals are bonded to each other through the residues of the coupling agent. Then, a part of the remainder of the vinyl aromatic hydrocarbon-conjugated diene compound block copolymer having active terminals remains unreacted in the solution. In the reaction using these coupling agents, the coupling rate can be controlled by, for example, producing the coupling agent and adding the coupling agent.

The polymerization method to be carried out in the polymerization step in the production method of the polymer of the present embodiment is not particularly limited and a known method can be applied. For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48- There can be mentioned the methods described in JP-A-2423, JP-A-48-4106, JP-A-56-28925, JP-A-59-166518, JP-A-60-186577 .

<Reactive agent>

In the polymerization process, a deflocculant may be added. The sealant is not particularly limited, but water or alcohol is known. Of these, alcohols are preferable from the viewpoint of deactivation efficiency. The deflocculant can be added at any timing of the polymerization process. If the amount of the deflocculating agent to be added is less than 100 mol% of the active terminal, the conjugated diene compound monomer and / or the vinyl aromatic hydrocarbon monomer can be continuously added after the addition of the deflocculating agent. By doing so, the polymerization reaction of the active terminal, which is not inactivated, with the conjugated diene compound monomer and / or the vinyl aromatic hydrocarbon monomer is continued to obtain a polymer solution containing a polymer having a different molecular weight.

When the component (A) and the component (B) are simultaneously produced, the content of the component (A) and the component (B) can be controlled by adjusting the molar amount of the addition initiator to the addition amount of the polymerization initiator have. As the molar amount of addition of the deflocculating agent is larger, the content of the component (A) increases, and when the molar amount of the deflocculating agent is smaller, the content of the component (B) tends to decrease.

The ratio of the weight average molecular weight and the weight average molecular weight of the component (A) and the component (B) can be controlled by adding the conjugated diene compound monomer and / or the vinyl aromatic hydrocarbon monomer after the addition of the deflocculant and continuing the polymerization reaction have. Specifically, the larger the amount of the conjugated diene monomer and / or the vinyl aromatic monomer to be added after the addition of the deflocculating agent, the larger the weight average molecular weight of the component (B) and the tendency of the weight average molecular weight accompanying the tendency.

(Hydrogen addition process)

The hydrogenation step is a step of converting a double bond in at least the conjugated diene compound monomer of the polymer obtained in the polymerization step into a hydrogenation product by a hydrogenation reaction. Specifically, a hydrogenated block copolymer solution can be obtained by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst. At that time, the hydrogenation rate of the block copolymer can be controlled by adjusting the reaction temperature, the reaction time, the hydrogen supply amount, the catalyst amount, and the like.

The catalyst to be used for the hydrogenation reaction is not particularly limited and includes, for example, (1) a supported heterogeneous catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on a carrier such as carbon, silica, alumina, (2) a so-called Ziegler-type catalyst using an organic salt such as Ni, Co, Fe, Cr or a reducing agent such as an acetylacetone salt and an organic Al, or an organometallic catalyst such as an organic metal compound such as Ru or Rh, Or a uniform catalyst using organic Li, organic Al, organic Mg or the like as a reducing agent for the titanocene compound is known. Among these, a homogeneous catalyst system using organic Li, organic Al, organic Mg or the like is preferably used as a reducing agent for the titanocene compound from the viewpoints of economy, polymer colorability or adhesion.

The hydrogenation reaction temperature is not particularly limited, but is preferably 0 to 200 占 폚, more preferably 30 to 150 占 폚. The pressure of hydrogen used in the hydrogenation reaction is not particularly limited, but is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, still more preferably 0.3 to 5 MPa. The hydrogenation reaction time is not particularly limited, but is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. In addition, the hydrogenation reaction may be a batch process, a continuous process, or a combination thereof.

Examples of the hydrogenation method include, but are not limited to, Japanese Patent Publication Nos. 42-8704, 43-6636, 63-4841, and 63-5401 And the method described in JP-A-2003-348701.

The hydrogenation reaction is not particularly limited, but from the viewpoint of high hydrogenation activity, it is preferable to carry out after the step of inactivating the active terminal of the polymer described later.

(Solvent removal step)

The solvent removal step is a step of removing the solvent of the solution containing the polymer. The solvent removal method is not particularly limited, and for example, there can be mentioned a method of removing solvent by a steam stripping method or a direct desolvation method.

The amount of the residual solvent in the polymer obtained by the above production method of the polymer is not particularly limited, but is preferably 2% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, Still more preferably 0.05 mass% or less, still more preferably 0.01 mass% or less.

From the viewpoints of heat aging resistance and gelation resistance of the hydrogenated block copolymer composition of the present embodiment, it is preferable to add an antioxidant. Examples of the antioxidant include, but are not limited to, a phenol-based antioxidant of a radical scavenger, a phosphorus-based antioxidant and a sulfur-based antioxidant to release the peroxide. In addition, an antioxidant having both performance can be used. These may be used alone, or two or more of them may be used in combination. Among them, it is preferable to add at least a phenol-based antioxidant from the viewpoints of heat aging resistance of the polymer and inhibition of gelation.

In addition, from the viewpoint of prevention of coloring of the polymer and high mechanical strength, it is possible to carry out a demining step for removing the metal in the polymer and a neutralization step for adjusting the pH of the polymer, for example, adding acid or carbonic acid gas.

The hydrogenated block copolymer composition of the present embodiment which can be produced as described above is a hydrogenated block copolymer composition in which a functional group containing a polar group containing an atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur and tin is bonded to a block copolymer, Or a modified block copolymer obtained by modifying a block copolymer component with a modifier such as maleic anhydride. Such a modified copolymer is obtained by subjecting the component (A) and the component (B) obtained by the above-mentioned method to a known denaturing reaction.

The method for imparting these functional groups is not particularly limited, and for example, a method of adding a functional group to a polymer using a compound having a functional group in an initiator, a monomer, a coupling agent or a stopper can be mentioned.

As the initiator containing a functional group, an initiator containing an N group is preferable, and examples thereof include dioctylaminolithium, di-2-ethylhexylaminolithium, ethylbenzylaminolithium, (3- (dibutylamino) Dino-lithium and the like.

Examples of the monomer containing a functional group include a compound containing a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group in the monomer used for the above-mentioned polymerization. Among them, monomers containing an N group are preferable, and N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis (trimethylsilyl) aminoethylstyrene, 1- (2-pyrrolidinoethyl) styrene, 4- (2-piperidinoethyl) styrene, 4- ( Styrene, 4- (2-thiazinoethyl) styrene, 4- (2-N-methylpiperazinoethyl) styrene, 1- ((4-vinylphenoxy) methyl) pyrrolidine, and 1- (4-vinylbenzyloxymethyl) pyrrolidine.

Examples of the coupling agent and the stopper containing a functional group include a compound containing a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group among the above coupling agents. Among them, a coupling agent containing an N group or an O group is preferable, and a coupling agent containing tetraglycidylmethoxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Silane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropyldiethylethoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl- Dinonon, N, N'-dimethylpropylene urea, N-methylpyrrolidone and the like.

[Point Adhesive Composition]

The viscous adhesive composition of the present embodiment contains 100 parts by mass of the hydrogenated block copolymer composition, 20 to 500 parts by mass of the tackifier, and 0 to 300 parts by mass of the softener. Such a viscous adhesive composition of the present embodiment has excellent adhesive force, tack and holding force, and is excellent in adhesion property, low viscosity property, texture, and balance among them.

It is also preferable that the point-adhesive composition of the present embodiment contains a polymer other than the component (A) and the component (B) (for example, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a hydrogenated styrene- Block copolymers, hydrogenated styrene-isoprene block copolymers, styrene-butadiene-isoprene block copolymers, hydrogenated styrene-butadiene-isoprene block copolymers, etc.). In this case, 20 to 500 parts by mass of a tackifier, which will be described later, and 0 to 300 parts by mass of a softening agent to be described later, per 100 parts by mass of the polymer and the total content of the components (A) and (B) And a mass portion.

It is also preferable to select the weight average molecular weight of the components (A) and (B) in the hydrogenated block copolymer composition and adjust the blending amount of each component such as a tackifier and a softener depending on the application.

(Tackifier)

The tackifier can be selected in various ways according to the intended use and the required performance of the resulting tackifier composition. Examples of the tackifier include, but are not limited to, natural rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, hydrogenated rosin , Pentaerythritol ester of hydrogenated rosin, and the like; Aromatic terpene resins, hydrogenated derivatives of aromatic modified terpene resins, terpene phenol resins, hydrogenated derivatives of terpene phenol resins, terpene resins (mono terpene, diterpene, triterpene, , Polypentene and the like), hydrogenated terpene resins, and the like; Aliphatic petroleum hydrocarbon resin (C5 series resin), hydrogenated derivative of aliphatic petroleum hydrocarbon resin, aromatic petroleum hydrocarbon resin (C9 series resin), hydrogenated derivative of aromatic petroleum hydrocarbon resin, dicyclopentadiene resin, dicyclopentadiene series resin A hydrogenated derivative of a resin, a hydrogenated derivative of a resin, a C5 / C9 copolymer resin, a hydrogenated derivative of a C5 / C9 copolymer resin, a cyclic aliphatic petroleum hydrocarbon resin, and a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin . These tackifiers may be used alone or in combination of two or more.

The tackifier may be a liquid-type tackifier resin having colorless to pale yellow color, substantially no odor, and good thermal stability.

Hereinafter, a preferable tackifier according to application and performance will be described in more detail.

(Tackifier of hydrogenated derivative)

From the viewpoint of difficulty in coloring and low odor, the tackifying resin is preferably a hydrogenated derivative. Examples of the hydrogenated derivatives include, but are not limited to, hydrogenated derivatives of rosin resins, hydrogenated derivatives of rosin ester, hydrogenated derivatives of aromatic modified terpene resins, hydrogenated derivatives of terpene phenol resin; Hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 series resins), hydrogenated derivatives of aromatic petroleum hydrocarbon resins (C9 series resins), hydrogenated derivatives of dicyclopentadiene resins, hydrogenated derivatives of modified dicyclopentadiene resins , Hydrogenated derivatives of C5 / C9 copolymer resins, and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins. Among these, a hydrogenated derivative of an aromatic petroleum hydrocarbon resin (C9 resin) and a hydrogenated derivative of a dicyclopentadiene resin are particularly preferable. The commercially available products of such hydrogenated derivatives include, but are not limited to, Alcon P90, Alcon P100, Alcon P115, Alcon P125, Alcon P140 (trade name), Alcon M90, Alcon M100, Alcon M115, Alcon M135 (Product name) manufactured by Eastman Chemical Co., Ltd., Rigalite R1010, Rigalite R1090, Rigalite R1100, Rigalite S5100, Rigalite R7100, Rigalite C6100 (trade name) East Tack C100W, East Tack C100L, East Tack C100R, East Tack C115W, East Tack C115R (trade name), Staferrite E (trade name), Foral AXE (trade name), Stearite Ester 10E (Trade name), Clearron K (trade name), YS Polystar UH (trade name), Exorhs 5340, Exorhs 5320, Eskorets 5300, Eskorets 5380, Eskorets 5400 , Escort (Quinton A100, Quinton B170, Quinton M100, Quinton R100, Quinton S195, Quinton D100, Quinton U185, Quinton DX395, Quinton 390N, Quinton N180, Quinton G100B, Quinton G100B, (Trade name) manufactured by Idemitsu Kosan Co., Ltd., Imab S100, Imab S110, Imab P100, Imab P125, Imab P140 (trade name), Rikapine And Rica Rosin F (trade name) manufactured by Tech.

(Tackifier other than the hydrogenated derivative)

The tackifier other than the hydrogenated derivative is not particularly limited, and examples of the tackifier include natural rosin, polymerized rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, Rosin esters such as pentaerythritol ester and the like; Copolymers of natural terpenes, three-dimensional polymers of natural terpenes, aromatic modified terpene resins, terpene phenol resins, terpene resins; Aliphatic petroleum hydrocarbon resin (C5 series resin), aromatic petroleum hydrocarbon resin (C9 series resin), dicyclopentadiene series resin, C5 / C9 copolymer series resin, and cyclic aliphatic petroleum hydrocarbon resin. Among these, aliphatic petroleum hydrocarbon resins (C5 series), aromatic petroleum hydrocarbon resins (C9 series resins), C5 / C9 copolymer resins, cyclic aliphatic petroleum hydrocarbon resins, terpene resins, natural and modified rosin esters and mixtures thereof are preferable. Examples of commercially available products include commercially available products such as ester gum AA-L, ester gum A, ester gum AAV, ester gum, ester gum 105, ester gum AT, benzene A, benzene AZ, benzene C, benzene D125, Wingtack 95, Wingtack 98, Wingtack EXTra, Wingtack RTT-7850, WingtackPLUS, WingtackET, WingtackSTS, Wingtack 86 (trade names), manufactured by CrayValley Co., (Trade name) manufactured by Eastman Chemical Co., Piccotac 8095, Piccotac 1095, Piccotac 1098, Piccotac 1100 (trade name) manufactured by Eastman Chemical, Eskorets 1102, Eskorets 1202, Eskorets 1204 LS, Eskorets 1304, Eskorets 1310, Eskorets 1315, Sylvagum (trade name) and Sylvalite (trade name), manufactured by Arizona Chemical Co., and Piccolyte (trade name), manufactured by Ashland Co., Ltd., Yasuhara Chemical Co., YS Polystar T (trade name), YS Polystar S (trade name), YS Polystar G (trade name), YS Resist PX (trade name), YS Resin PXN (Trade name), YS POLYSTAR K (trade name), YS POLYSTAR TH (trade name), YS resin TO (trade name), YS resin TR (trade name), YS resin SX (trade name), Maruzen Sekiyu Kagakusa Marcarets M (trade name) manufactured by Mitsubishi Chemical Corporation.

(Aliphatic tackifier)

It is preferable to use an aliphatic tackifier as a tackifier in order to obtain a tackifier composition having high tackiness and high holding power and economical efficiency. Examples of the aliphatic tackifier include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 resins), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 resins), C5 / C9 copolymer resins, C5 / A hydrogenated derivative of a total resin, a cyclic aliphatic petroleum hydrocarbon resin, and a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. The aliphatic tackifier is preferably an aliphatic hydrocarbon group content of 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 80% Is 88 mass% or more, and even more preferably 95 mass% or more. When the content of the aliphatic hydrocarbon group is within the above range, the tackiness, holding power, and economical efficiency tend to be further improved.

The aliphatic tackifier can be produced by homopolymerizing or copolymerizing a monomer having an aliphatic group and a polymerizable unsaturated group. Examples of the monomer having an aliphatic group and a polymerizable unsaturated group include, but are not limited to, natural and synthetic terpenes including C5 or C6 cyclopentyl or cyclohexyl groups. Examples of other monomers that can be used in the copolymerization include, but are not limited to, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, , 3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, terpene-phenol resin and the like.

(Aromatic tackifier)

From the viewpoint of obtaining a point adhesive composition having high adhesive force and high coatability, it is preferable to use an aromatic tackifier as the tackifier. The aromatic tackifier is not particularly limited, and examples thereof include an aromatic petroleum hydrocarbon resin (C9 resin) and a C5 / C9 copolymer resin. The aromatic tackifier is preferably at least 50 mass%, more preferably at least 70 mass%, even more preferably at least 80 mass%, and still more preferably at least 50 mass% Is 88 mass% or more, and more preferably 95 mass% or more. When the content of the aromatic hydrocarbon group is within the above range, the adhesive strength and the coating property tend to be further improved.

The aromatic tackifier can be produced by homopolymerizing or copolymerizing a monomer having an aromatic group and a polymerizable unsaturated group, respectively. Examples of the monomer having an aromatic group and a polymerizable unsaturated group include, but not limited to, styrene,? -Methylstyrene, vinyltoluene, methoxystyrene, TERT-butylstyrene, chlorostyrene, ). Examples of other monomers that can be used in the copolymerization include, but are not limited to, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, , 3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, terpene-phenol resin and the like. Examples of commercially available products include commercially available products such as Endex 155 (trade name), Christarex 1120, Christarex 3085, Christarex 3100, Christarex 5140, Christarex F100 (trade name), Plustrin 240, Plustrin 290, ) (Trade name).

(A tackifier having an affinity for a block of a glassy phase (for example, a polymer block (Ar) of a block copolymer and / or a block of a non-glassy phase (for example, a polymer block (D)

As the point-adhesive composition, it is preferable to have a high adhesive property, a low change in adhesive strength with time, a low creep property (good value with a small value), a low melt viscosity, a high heat resistance, , 20 to 75 mass% of a tackifier having affinity to a non-glass block (for example, a polymer block (D), usually an intermediate block) of the block copolymer contained in the tackifier composition, More preferably 0.1 to 30% by mass of a tackifier having affinity to the glassy block (for example, the polymer block (Ar), usually the outer block) of the aggregate. Here, the block copolymer is a concept including components (A) and (B).

The tackifier having affinity to the non-glass block (for example, polymer block (D)) of the block copolymer is not particularly limited, and examples thereof include rosin compounds, terpene compounds, aliphatic petroleum hydrocarbon resins C5 type resin), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins, C5 / C9 copolymer resins, hydrogenated derivatives of C5 / C9 copolymer resins, cyclic aliphatic petroleum hydrocarbon resins, and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins. .

The content of the tackifier having affinity to the non-glassy phase of the block copolymer is preferably 20 to 75% by mass, more preferably 25 to 70% by mass, relative to 100% by mass of the pressure-sensitive adhesive composition Is from 30 to 65% by mass.

The tackifier having affinity to a glass block (for example, polymer block (Ar)) of the block copolymer is not particularly limited, but for example, a resin having an aromatic ring in the molecule is preferable. Such a resin is not particularly limited, and examples thereof include an aromatic group-containing resin such as a homopolymer or a copolymer containing vinyltoluene, styrene,? -Methylstyrene, coumarone, or indene as a constitutional unit. Of these, Christalex and Plustrin having alpha -methylstyrene, Pycotex (trade name, product of Eastman Chemical Co., Ltd.) and the like are preferable.

The content of the tackifier having affinity to the glassy block of the block copolymer is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, and still more preferably from 1 to 20% by mass, based on 100% By mass to 2% by mass.

From the viewpoint of obtaining a point adhesive composition having a high initial adhesion, high wettability, low melt viscosity or high coatability, it is preferable to use a petroleum resin having an aromatic content of 3 to 12 mass% as the tackifier. Examples of such petroleum resins include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 series resin), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 series resin), aromatic petroleum hydrocarbon resins (C9 series resin) Hydrogenated derivatives of a hydrocarbon resin (C9 resin), dicyclopentadiene resins, hydrogenated derivatives of dicyclopentadiene resins, C5 / C9 copolymer resins, hydrogenated derivatives of C5 / C9 copolymer resins, Petroleum hydrocarbon resins, and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins. The aromatic content of the petroleum resin is preferably 3 to 12 mass%, and more preferably 4 to 10 mass%. Among these, a petroleum resin with hydrogenation is particularly preferable.

From the viewpoint of obtaining a point-adhesive composition having high initial adhesion, high wettability, low melt viscosity or high coatability, it is preferable to use styrene oligomer as the tackifier. Examples of the styrene oligomer include aromatic petroleum hydrocarbon resins (C9 series resin) such as Piccolastic A5 (trade name) and Piccolastic A75 (Eastman Chemical Co., Ltd.), though there is no particular limitation.

The content of the styrene oligomer is preferably 35 mass% or less, more preferably 30 mass% or less, and further preferably 25 mass% or less, based on 100 mass% of the viscous adhesive composition.

From the viewpoint of obtaining a point-adhesive composition having high odor characteristics, high weatherability, high transparency, colorlessness, low heat discoloration and the like, a hydrogenated resin (for example, the hydrogenated derivative) Is preferably used.

The content of the tackifier is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 75 parts by mass or more, relative to 100 parts by mass of the hydrogenated block copolymer composition Or more. The content of the tackifier is not more than 500 parts by mass, preferably not more than 400 parts by mass, and not more than 350 parts by mass based on 100 parts by mass of the block copolymer composition. The content of the tackifier is 20 to 500 parts by mass, preferably 30 to 400 parts by mass, more preferably 50 to 350 parts by mass, relative to 100 parts by mass of the block copolymer composition, 75 to 350 parts by mass. When the content of the tackifier is within the above range, the tack property is further improved.

When the viscous adhesive composition of the present embodiment contains a polymer other than the components (A) and (B) to be described later, the content of the tackifier is preferably 100 parts by mass in total of the polymers contained in the viscous adhesive composition Is at least 20 parts by mass, preferably at least 30 parts by mass, more preferably at least 50 parts by mass, and even more preferably at least 75 parts by mass. The content of the tackifier is not more than 500 parts by mass, preferably not more than 400 parts by mass and not more than 350 parts by mass based on 100 parts by mass of the total amount of the polymers contained in the adhesive composition. When the content of the tackifier is within the above range, the tack property is further improved.

Here, the polymer contained in the viscous adhesive composition refers to the component (A), the component (B), the vinyl aromatic elastomer, the conjugated diene rubber, and the natural rubber described below.

(Softener)

The term &quot; softening agent &quot; refers to a material having a function of lowering the hardness of the viscous adhesive composition and lowering the viscosity. Examples of the softener include, but are not limited to, petroleum oils such as known paraffinic process oils, naphthenic process oils, aromatic process oils, extender oils, and mixed oils thereof; Vegetable oil; Plasticizers; Synthetic liquid oligomers; And mixtures thereof.

Hereinafter, a preferred softening agent depending on the application and performance will be described in more detail.

From the viewpoint of lowering the viscosity of the viscous adhesive composition, improving the tackiness, and lowering the hardness, oils can be used. The oils are not particularly limited and include, for example, known paraffinic process oils, naphthenic process oils, aromatic process oils, extender oils, and mixed oils thereof. Paraffinic process oil is preferable from the viewpoints of low temperature characteristics, aging resistance, stain resistance and color tone, and aromatic process oil is preferable from the viewpoint of compatibility, and from the viewpoint of balance of low temperature property, aging resistance, stain resistance, color tone and compatibility Naphthenic process oil is preferred.

When a dermabrasive composition is used as a percutaneous absorption preparation, a plasticizer can be used as a softening agent from the viewpoints of improving percutaneous absorption properties and storage stability and improving drug solubility in the dermabrasant composition. The plasticizer is not particularly limited, and examples thereof include liquid paraffin; A fatty acid ester containing a higher fatty acid having 12 to 16 carbon atoms and a lower monohydric alcohol having 1 to 4 carbon atoms, such as isopropyl myristate, ethyl laurate and isopropyl palmitate; A fatty acid having 8 to 10 carbon atoms; Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol; Oils such as olive oil, castor oil, squalane, and lanolin; Examples of the solvent include alcohols such as ethyl acetate, ethyl alcohol, dimethyl decyl sulfoxide, decyl methyl sulfoxide, dimethyl sulfoxide, dimethyl formamide, dimethylacetamide, dimethyl laurylamide, dodecylpyrrolidone, isosorbitol, oleyl alcohol, Organic solvent; Liquid surfactant; Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, methyl stearyl alcohol, ethoxylated stearyl alcohol, glycerin ester, myristic acid isotridecyl, N-methylpyrrolidone, . Of these, liquid compounds at room temperature are used. Of these, glycerin esters are preferable, and medium chain fatty acid triglycerides, which are esters of fatty acids having 8 to 10 carbon atoms and glycerin, are more preferable. Examples of the medium chain fatty acid triglyceride include tri (caprylic / capric) glyceryl. The plasticizer may be used alone or in combination of two or more.

When the pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape are used as pressure-sensitive adhesive tapes for medical use such as taping tapes, it is preferable to use liquid paraffin in combination with other plasticizers.

When the point adhesive composition and the adhesive tape are used for medical applications, the amount of the plasticizer to be added is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, relative to 100% by mass of the adhesive composition By mass to 3% by mass to 10% by mass. When the addition amount of the liquid plasticizer is 3 mass% or more, the percutaneous absorption property, storage stability, and drug solubility in the adhesive composition tend to be further improved. Further, when the addition amount of the liquid plasticizer is 20 mass% or less, the cohesive force of the pressure-sensitive adhesive composition tends to be further improved.

When it is desired to make the viscous composition more smooth, a synthetic liquid oligomer can be used from the viewpoint of improvement in bleeding property. The synthetic liquid oligomer may be also referred to as a liquid rubber, and is not particularly limited, and examples thereof include styrene oligomer, butadiene oligomer, isoprene oligomer, butene oligomer, and isobutylene oligomer.

When a natural-derived ingredient is desired to be used as a softening agent, a vegetable oil is used. The vegetable oil is not particularly limited, and examples thereof include castor oil, tall oil, and pine tar. From the viewpoint of cold tolerance, castor oil is preferable.

Examples of the plasticizer include, but are not limited to, dibasic acid esters such as DBP and DOP.

Examples of commercially available products of such softening agents include, but are not limited to, Diana Frescia S32, Diana Process Oil PW-32, PW-90, PW-150, PS-430 and Diana Process Oil NP-24 manufactured by Idemitsu Kosan Co., , NR-26, NR-68, NS-90S, NS-100, NM-280, Diana Process Oil AC-12, AC-640, AH-16, AH-24, AH- , DN Oil KP-68 (trade name) manufactured by BP Chemical Co., Enerper M1930 (trade name) manufactured by BP Chemical Co., Register (trade name) manufactured by Crompton, Primol352 (trade name) manufactured by Esso Corporation, KN4010 N-60, N-70, N-75, N-80, Shin Takk PA-95, PA-100, PA-140, Shin Takk HA- JOMO process P200, P300, P500, 750, JOMO process R25, R50, R200, R1000, JOMO process X50, X100E, X140 (trade name) Sekisui emulsion waves 110, 115, 120, 130, 150, 2100, 2280, P-100, P-200, P-200, Nitofrene 720L (trade name) manufactured by Fuji Kogyo Co., Shell Flex 371JY (manufactured by Shell Japan), P-400, P-400, P-500, Foot Callouflex 1060W, 1060E, 1150W, 1150E, 1400W, 1400E, 2040E, 2050N, Footcol Aromax 1,3,5, EXP1 3, PN-3M, PN-3N-H (trade name), Petrex process oil LPO-R, LPO-V, PF-2 (trade name) Cosmo process 40, 40A, 40C, 200A, 100, 1000 (trade name) of Sekiyu ruby reductans.

The content of the softening agent is 0 to 300 parts by mass, preferably 10 to 175 parts by mass, and more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the block copolymer composition. When the content of the softening agent is within the above range, the point-sticking property is further improved.

The content of the softening agent is preferably 35 mass% or less, more preferably 3 mass% or more and 30 mass% or less, with respect to the point adhesive composition. When the content of the softening agent is within the above range, the point-sticking property is further improved.

When the viscous adhesive composition of the present embodiment contains a polymer other than the components (A) and (B) to be described later, the content of the softener is preferably from 0 to 100 parts by mass based on 100 parts by mass of the total of the polymers contained in the adhesive composition. To 300 parts by mass, preferably 10 to 175 parts by mass, and more preferably 20 to 150 parts by mass. When the content of the softening agent is within the above range, the point-sticking property is further improved.

(Other components)

The pressure-sensitive adhesive composition of the present embodiment may contain a polymer other than the component (A) and the component (B), a wax, a polar group-containing polymer, a stabilizer and a particulate filler, if necessary.

(Polymer other than the component (A) and the component (B)).

Polymers other than the component (A) and the component (B) are not particularly limited, and examples thereof include polyolefins, polyolefin copolymers, vinyl aromatic elastomers and other rubbers. In the present specification, "other than the components (A) and (B)" means that the component (A) and the component (B) do not correspond.

The content of the polymer other than the component (A) and the component (B) is not limited, but the total amount of the component (A) and the component (B) ) Relative to 100 parts by mass of the total amount of the polymer other than the polymer (A). The total amount of the component (A) and the component (B) may be 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, Or more. Further, it is not necessary to include a polymer other than the component (A) and the component (B).

Examples of the polyolefin and polyolefin-based copolymer include, but are not limited to, a copolymer of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- A polymer containing two or more kinds of monomers, an atactic polypropylene, and an ethylene-ethyl acrylate copolymer. Examples of commercially available products of polyolefins include VESTOPLAST 408, VESTOPLAST 508, VESTOPLAST 703, VESTOPLAST 704 and VESTOPLAST 708 (trade name) manufactured by Degussa, and Licocene PP1302, Licocene PP1502, Licocene PP1602 and Licocene PP2602 (trade names) manufactured by Clariant Japan .

Examples of the vinyl aromatic elastomer include, but are not limited to, styrene-ethylene block copolymer, styrene-butadiene block copolymer, styrene-propylene block copolymer, styrene-isoprene block copolymer, styrene- Butadiene-isoprene block copolymer, and the like, and the component (A) and the component (B) other than the component (A), the hydrogenated styrene-isoprene block copolymer and the hydrogenated styrene- Of polymers.

Examples of commercially available styrene-isoprene block copolymers include Quintex 3421, Quintex 3620, Quintex 3433N, Quintax 3520, Quintax 3450, Quintax 3270, Quintax 3280, Quintax 3390 (trade name) D1111P, D1113P, D1114PX, D1117P, D1119P, D1124P, D1128PX, D1193P and D4433P (trade names) manufactured by Kraton Polymer, vectors 4111A, 4111N, 4113A, 4113N, 4114A and 4114N As a commercial product of the styrene-butadiene block copolymer, there are commercially available products such as a vector 4186A, a vector 4187A, a vector 4211A, a vector 4211N, a vector 4213A, a vector 4213N, a vector 4215A, a vector 4230, a vector 4293A, a vector 4411A The vector 2336, the vector 2411, the vector 2411P, the vector 2518, the vector 2518A, the vector 2518LD, and the vector 2518P (trade names) manufactured by TSRC Co., , Vector 2518PC, vector, vector 6241A, vector 7400, vector 8508, vector 8508A, taipole 3201, taipole 3206, taipole 4 Toughprene A, toughprene 125, toughprene 126S, toughprene 315P, asaprene T411, asaprene T412, asaprene T413, and asaprene T420 (trade name) manufactured by Asahi Kasei Chemicals Co., , Asaprene T432, asaprene T436, asaprene T437, asaprene T438, and asaprene T439 (trade name). G1701, G1702, G1750X, G1765X, and G1780X (trade names) manufactured by Kraton Polymer Co., Ltd., Septon 1001, Septon 1020, Septon 2002, Septon 2004, Septon 2006, Septon 2007, Septon 2063, Septon 2104 (trade name), and the like. Examples of commercially available hydrogenated styrene-butadiene block copolymers include G1643, G1645, G1650, G1651, G1652, G1654, G1657 and G1726 (trade names) manufactured by Kraton Polymer, Septon 8004, Septon 8006, Septon 8007, H1021, H1062, H1052, H1041, H1051 (trade name) manufactured by Asahi Kasei Chemicals Co., Ltd., , H1057, H1043, N504 (trade name). Commercially available products of the hydrogenated styrene-butadiene-isoprene block copolymer include Septon 4033, Septon 4044, Septon 4055, Septon 4077, and Septon 4099 (trade name) manufactured by Kuraray Co., Ltd.

The content of the vinyl aromatic elastomer other than the component (A) and the component (B) is 100 parts by mass in total of the block copolymer other than the component (A), the component (B) and the component (A) , Preferably from 5 to 95 parts by mass, more preferably from 10 to 90 parts by mass, and still more preferably from 15 to 85 parts by mass.

Examples of the other rubber include, but not limited to, natural rubber; Synthetic rubbers such as isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, propylene-butylene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber and polypentenam rubber . Of these, natural rubber is preferable from the viewpoints of crosslinkability and economical efficiency.

By using a natural rubber, the crosslinking property of the viscous adhesive composition is further improved, and the economic efficiency tends to be excellent.

When the natural rubber is contained, the content thereof is preferably 3 to 90 mass%, more preferably 10 to 80 mass%, and still more preferably 15 to 75 mass%, based on 100 mass% of the viscous adhesive composition . When the content of the natural rubber is within the above range, the crosslinking property, heat resistance, solvent resistance, and economical efficiency of the viscous adhesive composition tend to be further improved.

Hereinafter, polymers other than the preferred components (A) and (B) according to the application and performance will be described in more detail.

(Hydrogenated vinyl aromatic elastomer)

From the viewpoints of reducing the amount of adhesive residue remaining when adhering the adhesive composition to an adherend and detaching it, suppressing the adhesive strength of the adhesive composition from deteriorating over time or creeping property (having a smaller value), heat resistance, weather resistance, A hydrogenated vinyl aromatic elastomer may be used. Examples of the hydrogenated vinyl aromatic elastomer include hydrogenated styrene-butadiene block copolymer having a structure such as S-EB-S (S: polystyrene block, EB: ethylene / butylene copolymer block) coalescence; A hydrogenated styrene-isoprene block copolymer having a structure such as S-EP-S (S: polystyrene block, EP: ethylene / propylene copolymer block); And a hydrogenated styrene-butadiene-isoprene block copolymer having a structure such as S-EEP-S (S: polystyrene block, EEP: ethylene / ethylene / propylene copolymer block). Of these, hydrogenated styrene-butadiene block copolymers and hydrogenated styrene-isoprene block copolymers are preferred.

The styrene content of the hydrogenated vinyl aromatic elastomer is preferably 10% by mass to 45% by mass, more preferably 13% by mass to 40% by mass, relative to 100% by mass of the hydrogenated vinyl aromatic elastomer, Is 15 mass% to 35 mass%.

The content of the polystyrene block in the hydrogenated vinyl aromatic elastomer is preferably 30 mass% or less, more preferably 21 mass% or less, and further preferably 15 mass% or less based on 100 mass% of the hydrogenated vinyl aromatic elastomer. % Or less. When the content of the polystyrene block is within the above range, the flexibility and compatibility tends to be further improved.

The content of B in the ethylene / butylene copolymer block in the hydrogenated vinyl aromatic elastomer is preferably as high as possible, more preferably not less than 35 mol% based on 100 mass% of the hydrogenated vinyl aromatic elastomer, Is 45 mol% or more, more preferably 55 mol% or more, and particularly preferably 60 mol% or more. When the content of B in the ethylene / butylene copolymer block is within the above range, the flexibility and compatibility tends to be further improved.

The hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the hydrogenated vinyl aromatic elastomer is preferably more than 90 mol%.

(Other partially hydrogenated vinyl aromatic elastomer)

It is preferable to use other partially hydrogenated vinyl aromatic elastomers from the viewpoints of adjusting the cohesive strength, adhesive strength, tack, and T (ODT) (order disorder transition temperature) of the adhesive composition. By adjusting the T (ODT) (ordered disorder transition temperature), the melt viscosity can be adjusted. The other partially hydrogenated vinyl aromatic elastomer includes a polymer block composed mainly of at least one vinyl aromatic hydrocarbon and a polymer block composed mainly of at least one conjugated diene compound and having an unsaturated double bond based on a conjugated diene compound Means that the hydrogenation ratio H (%) is 5 to 90 mol%, and the maximum value of the loss coefficient tan? At -100 DEG C to 0 DEG C is less than 0.4.

(Non-hydrogenated vinyl aromatic elastomer)

As the point adhesive composition, a non-hydrogenated vinyl aromatic elastomer can be used from the viewpoints of having high flexibility, high adhesiveness, suppressing gelation, and high economical efficiency. Examples of the non-hydrogenated vinyl aromatic elastomer include, but are not limited to, styrene-ethylene block copolymers; Styrene-butadiene block copolymer having a structure such as SBS, (SB) _n X (S: polystyrene block, B: polybutadiene block, X: Styrene-propylene block copolymers; Styrene-isoprene block copolymer having a structure such as SIS, (SI) _n X (S: polystyrene block, I: polyisoprene block, X: (I / B) _n X, S- (I / B) -S (S: polystyrene block, I / B: isoprene / butadiene copolymer block (even if isoprene and butadiene are alternately arranged at an arbitrary ratio And the proportion thereof may not be constant), and X: a residue of a coupling agent). The styrene-butadiene-isoprene block copolymer can be exemplified. Among them, the _{(SI) n X, (SB} ) n X, (S- (I / B)) n X , and more preferably having a radial structure. These may be used singly or in combination of two or more.

The styrene content of the non-hydrogenated vinyl aromatic elastomer is preferably 45 mass% or less based on 100 mass% of the non-hydrogenated vinyl aromatic elastomer.

The content of the diblock (for example, SB, SI, SBX, SIX) of the non-hydrogenated vinyl aromatic elastomer is preferably 10 to 80 mass% with respect to 100 mass% of the non-hydrogenated vinyl aromatic elastomer .

(Isoprene block copolymer)

As the point adhesive composition, an isoprene block copolymer having a non-hydrogenated isoprene monomer unit can be used from the viewpoint of providing excellent tack or from the viewpoint of economy. (SI) nS, (SI) nX (S: polystyrene block, I: polyisoprene block, n: an integer of 1 or more, preferably, Is an integer of 1 to 6, and X is a residue of a coupling agent), and the like. These may be used singly or in combination of two or more.

The styrene content of the isoprene block copolymer is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less based on 100% by mass of the isoprene block copolymer. More preferably, it is 18 mass% or less.

(Conjugated diene rubber)

The conjugated diene rubber can be used from the viewpoints of workability, low melt viscosity at 180 占 폚 or less, good tack, adhesive strength, adhesiveness, and die cuttability. Examples of the conjugated diene rubber include isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, and propylene-butylene rubber.

As the adhesive composition for adhesive tape, polybutadiene rubber or polyisoprene rubber can be used from the viewpoint of improving the self-back surface adhesion and skin adhesion. Of these, polyisoprene rubber is more preferable. The addition amount of the polybutadiene rubber and the polyisoprene rubber is preferably 3 to 25 mass%, more preferably 5 to 20 mass%, and still more preferably 5 to 15 mass%, based on 100 mass% of the point adhesive composition . When the addition amount of the polybutadiene rubber and the polyisoprene rubber is 3 mass% or more, the back surface adhesion and the skin adhesion force tend to be further improved. Further, when the addition amount of the polybutadiene rubber and the polyisoprene rubber is 25 mass% or less, the cohesive force is further improved and the tacky agent residue tends to be further suppressed.

As the conjugated diene rubber, a conjugated diene-based diblock copolymer can be used from the standpoints of processability of a point-adhesive composition, low melt viscosity at 180 ° C or less, good tack, adhesive strength, and adhesiveness. Examples of the conjugated diene diblock copolymer include polymers having a structure such as S-I, (S-I) X, S-B, and (S-B) X, and hydrogenated products thereof. These may be used singly or in combination of two or more, and may be liquid or solid at room temperature.

The content of the conjugated diene rubber is preferably 3 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 75% by mass, based on 100% by mass of the viscous adhesive composition. When the content of the conjugated diene rubber is within the above range, the oil-releasing property, the low melt viscosity, the tack, the adhesive strength, the adhesion and the flexibility of the viscous composition tend to be further improved.

(Ionomer)

When a low-temperature coating property, a low creep property, a high strength or a high shininess are required as the point-adhesive composition, the polymer can be used in the form of an ionomer. The ionomer is not particularly limited, but is preferably a homopolymer or copolymer comprising a carboxylate, a sulfonate or a phosphonate which is neutralized or partially neutralized by a metal ion, for example. The content of the ionomer is preferably 5% by mass or less based on the total amount of the pressure-sensitive adhesive composition.

(Polyolefin resin)

From the standpoint of imparting high-temperature storage stability and high shininess, or reducing the amount of the tackifier resin in the tackifier composition (not more than 55 mass% in the composition, and further not more than 45 mass%), Can be used. The polyolefin-based resin is not particularly limited, and for example, a copolymer of an alpha -olefin and an olefin or a propylene homopolymer is preferably used. The melting point (condition: DSC measurement, 5 占 폚 / min) of these polymers is preferably 110 占 폚 or lower, more preferably 100 占 폚 or lower, and still more preferably 60 占 폚 to 90 占 폚. These polymers may be resins or elastomers.

Further, from the viewpoint of the creep performance (the smaller the value is), the olefin elastomer having a block is more preferable. The molecular weight distribution of these polymers is preferably 1 to 4, more preferably 1 to 3. Further, from the viewpoint of workability, it is more preferable to use two or more kinds of corresponding polymers in combination. Concretely, it is preferable to use 30,000 to 60,000 and 60,000 to 90,000 polymers in combination, and it is more preferable to use at least 35,000 to 55,000 and 60,000 to 80,000 polymers in combination.

(Liquid component)

The point adhesive composition using a polyolefin-based resin preferably contains a liquid component (such as oil). The content of the liquid component is preferably 20% by mass or more, and more preferably 25% by mass or more, based on 100% by mass of the viscous adhesive composition. When elongation is required, it is preferable to use an olefinic elastomer in combination, and it is more preferable to use an olefinic elastomer having a Tg of -10 DEG C or lower in combination.

(Wax)

The pressure-sensitive adhesive composition may contain a wax if necessary. The addition amount of the wax is preferably 20 mass% or less, more preferably 2 to 10 mass%, and still more preferably 5 to 10 mass%, based on 100 mass% of the viscous adhesive composition. When the addition amount of the wax is within the above range, the melt viscosity, particularly the melt viscosity at 140 캜 or lower, tends to be further lowered.

The wax is not particularly limited, and examples thereof include paraffin wax, microcrystalline wax, and Fischer-Tropsch wax. By using such a wax, the melt viscosity, particularly the melt viscosity at 140 캜 or lower, tends to be further lowered.

The melting point of the wax is preferably 50 占 폚 or higher, more preferably 65 占 폚 or higher, still more preferably 70 占 폚 or higher, even more preferably 75 占 폚 or higher. The melting point of the wax is preferably 110 DEG C or less. When the melting point of the wax is within the above range, the melting viscosity, particularly the melting viscosity at 140 캜 or lower, tends to be lowered.

The softening point of the tackifier used in combination with the wax is preferably 70 占 폚 or higher, and more preferably 80 占 폚 or higher. G 'of the resulting pressure-sensitive adhesive composition in this case (measurement conditions: 25 ° C, 10 rad / s) is preferably 1 MPa or less, and the crystallization temperature is preferably 7 ° C or less.

Examples of commercial waxes that can be used include commercially available waxes such as trade name "115", trade name "120", trade name "125", trade name "130" HNP-11 ", trade name" HNP-12 ", trade name" HNP-9 ", trade name" HNP- SP-3035 &quot;, trade name &quot; SP-0140 &quot;, trade name &quot; SP- Hi-Mic-1070 ", trade name" Hi-Mic-1080 ", trade name" Hi-Mic-1090 " Hi-Mic-2065 ", trade name" Hi-Mic-2095 "manufactured by Tosoh Corporation," UltraScan 7A55A "manufactured by Tosoh Corporation, trade name" A-C540 " A-C540A &quot;, trade name &quot; A-C580 & A-C405 (M) &quot;, trade name &quot; A-C405 (T) &quot;, trade name &quot; A-C405 -C645P ", trade name" A-C573A ", trade name" A-C573P "and the like.

(Polar group-containing polymer)

The pressure-sensitive adhesive composition may contain a polar group-containing polymer containing an atom selected from the group consisting of nitrogen, oxygen, silicon, phosphorus, sulfur, tin and the like, if necessary. Examples of the polar group-containing polymer include, but not particularly limited to, a so-called modified polymer bonded to a block copolymer, a modified block copolymer obtained by modifying the block copolymer component with a modifier such as maleic anhydride, , Carboxylic acids, carboxylic anhydrides, and the like. By using the polar group-containing polymer, it is possible to further improve the viscous adhesion properties to an adherend having a high SP value such as a super absorbent polymer (SAP), an acrylic resin, a vinyl chloride resin, a nylon resin, There is a tendency.

Examples of commercially available products include HG252 (trade name) manufactured by Kuraray Co., Ltd., M1943, M1911, M1913, MP10, toughprene 912 (trade name), and Taipol 7131 (trade name) manufactured by Asahi Kasei Chemicals Corporation.

(stabilizator)

The pressure-sensitive adhesive composition may contain a stabilizer, if necessary. The "stabilizer" is added to improve the stability of the hot melt adhesive by preventing the hot melt adhesive from lowering in molecular weight due to heat, gelation, coloring, generation of malodor, and the like, and is not particularly limited.

As the stabilizer, for example, an antioxidant and a light stabilizer can be exemplified. Antioxidants and light stabilizers are generally used in disposable products and may be used as long as they can obtain the intended disposable product to be described later, and are not particularly limited.

(Antioxidant)

The &quot; antioxidant &quot; can be used, for example, to prevent oxidation deterioration of the hot melt adhesive. Examples of the antioxidant include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4'- Butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'- Methylphenylacrylate, 2,4-bis [(octylthio) methyl] -0-cresol, 2-t-butyl- 2- [1- (2-hydroxy-3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, Di-tert-pentylphenyl)] acrylate; Sulfur-based antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate, and pentaerythritol tetrakis (? - lauryl thiopropionate); Phosphorus antioxidants such as tris (nonylphenyl) phosphite and tris (2,4-di-t-butylphenyl) phosphite. These may be used alone or in combination of two or more.

Specific examples of commercially available products of antioxidants include Sumilizer GM (trade name), Smilayer TPD (trade name) and Smiliger TPS (trade name) manufactured by Sumitomo Chemical Industry Co., Ltd., Irganox 1076 (trade name) manufactured by Ciba Specialty Chemicals (Trade name), Irganox 1010 (trade name), Irganox HP2225FF (trade name), Irgafos 168 (trade name) and Irganox 1520 (trade name), and JOHOKU KAGAKUSA JF77 .

The content of the antioxidant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the viscous adhesive composition.

(Light stabilizer)

The &quot; light stabilizer &quot; can be used, for example, to improve the light resistance of a hot melt adhesive (change in low point adhesive properties after UV irradiation). Examples of the light stabilizer include, but are not limited to, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'- Benzotriazole-based ultraviolet absorbers such as benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole; Benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone; Triazine type ultraviolet absorber; Hindered amine light stabilizers; And a lactone type stabilizer: HALS. These may be used alone or in combination of two or more.

Specific examples of commercially available light stabilizers include Tinuvin P (trade name), Tinuvin 770DF (trade name), Cimassorb 2020FDL (trade name), ADEKA STAB LA-52 (trade name) -57 (trade name), and ADEKA STAB LA-77Y (trade name).

The content of the light stabilizer in the viscous adhesive composition of the present embodiment is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.07% by mass or more in view of high light resistance.

The content of the photocatalyst in the viscous adhesive composition of the present embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably 0.3% by mass or less in terms of suppression of bleeding of the light- desirable.

From the viewpoint of higher light resistance, it is preferable to further use the above antioxidant in combination with the above-described light-emitting agent.

Among antioxidants, from the viewpoint of higher light resistance, it is preferable to use at least a phosphorus antioxidant in addition to the above-described photostabilizer.

The content of the antioxidant in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, and still more preferably 0.06% by mass or more from the viewpoint of high light resistance.

The content of the photocatalyst in the viscous adhesive composition of the present embodiment is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less, from the viewpoints of suppression of bleeding of the antioxidant and economical efficiency.

(Particulate filler)

The pressure-sensitive adhesive composition may contain a particulate filler, if necessary. Examples of the particulate filler include, but are not limited to, mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, zinc oxide, Silica gel, diatomaceous earth, barium sulfate and the like. These shapes are preferably spherical, and their dimensions (diameter in the case of spherical shape) are not particularly limited.

[Characteristics of the pressure-sensitive adhesive composition]

The performance of the pressure-sensitive adhesive composition of the present embodiment can be measured in accordance with the measurement conditions shown in the examples using an adhesive tape manufactured under the conditions shown in the following examples.

G 'of the point-adhesive composition (measurement conditions: 25 DEG C, 10 rad / s) is preferably 20,000 or less, and more preferably 15,000 or less. When G 'of the point adhesive is within the above range, the residual amount of the adhesive in the point adhesive composition tends to be further reduced.

The content of the liquid diluent is preferably 60 mass% or less based on 100 mass% of the viscous adhesive composition. When the content of the liquid diluent is within the above range, it is particularly useful for skin application of an adhesive containing a percutaneous drug delivery application.

The adhesive composition of the present embodiment is also applicable to paper processing, bookbinding, disposable products and the like. Among them, since it is excellent in adhesion in the wet state, it is suitable for disposable products. Disposable products include woven, nonwoven, rubber, resin, paper, polyolefin film, polyester film, PVC film, ionomer film, PVDC film, PVA film, PC film, PS film, PAN film, PEN film, A film, a polyimide film, an EMAA film, and an EVOH film by applying a solution coating or a hot melt coating to a point-adhesive composition. The polyolefin film is preferably a polyethylene film or a polypropylene film for reasons of durability and cost. In addition, kraft paper is preferable for reasons of durability and cost, and kraft paper in which polyethylene is laminated from the viewpoints of durability and water resistance is preferable.

The melt viscosity of the hot melt point adhesive for disposable products for sanitary materials is preferably 5000 mPa · s or less, more preferably 400 to 3500 mPa · s, and even more preferably 800 to 3000 mPa · s at 150 ° C. The melting point is the viscosity of the melt of the hot-melt point adhesive and is measured by a Brookfield RVT type viscometer (spindle No. 27). Since the melt viscosity is in the above range, the hot-melt point adhesive is suitable for low-temperature coating, uniformly applied to the nonwoven fabric, and easy to penetrate, making it particularly suitable as a hot melt adhesive for disposable products for sanitary materials.

Disposable products for sanitary materials are not particularly limited, and examples thereof include paper diapers, sanitary napkins, pet sheets, hospital gowns, and surgical bags.

[Method for producing a pressure-sensitive adhesive composition]

The pressure-sensitive adhesive composition of the present embodiment can be prepared by mixing the above-mentioned hydrogenated block copolymer composition, the tackifier, a softening agent and other components as necessary by a known method. The mixing method is not particularly limited, and for example, a method in which the block copolymer composition, the tackifier, and the softener are uniformly mixed while being heated with a mixer or a kneader.

The temperature at the time of mixing is preferably 130 占 폚 to 220 占 폚, more preferably 140 占 폚 to 210 占 폚, and still more preferably 150 占 폚 to 200 占 폚. When the temperature at the time of mixing is 130 占 폚 or higher, the block copolymer composition can be sufficiently melted and the dispersion tends to be good. When the temperature at the time of mixing is 220 占 폚 or lower, there is a tendency that evaporation of the low molecular weight component of the crosslinking agent and the tackifier can be prevented and the deterioration of the point-adhesive property can be prevented.

[Method of applying the pressure-sensitive adhesive composition]

When the adhesive composition is applied and used, the application method is not particularly limited as long as a desired product can be obtained. For example, a method of dissolving the adhesive composition in a solvent and coating the solution, Hot-melt coating method in which the coating is performed by melting and coating.

Among them, the hot-melt coating method is preferable because of environmental pollution and ease of coating. The hot-melt coating method is largely classified into contact coating and non-contact coating. &Quot; Contact application &quot; refers to a coating method in which a sprayer is brought into contact with a member or film when a hot melt adhesive is applied. The &quot; noncontact coating &quot; refers to a coating method in which a sprayer is not brought into contact with a member or a film when a hot melt adhesive is applied. The contact coating method is not particularly limited, and examples thereof include a slot coater coating and roll coating, a die coating coating, a porous coating coating in a porous form, and a pattern coating. The noncontact coating method is not particularly limited. For example, the noncontact coating method is not particularly limited. For example, the noncontact coating method includes a spiral coating method in which an adhesive can be applied in an air spiral manner by intermittent or continuous coating, an omega coating method, It is possible to apply a slot spray coating or a curtain spray coating which can be applied in a plane shape, a dot coating which can be applied in a dot shape, a bead coating which can be applied in a linear shape, a forming melt coating which foams a hot melt, , Spray coating in a mist state, and the like.

Conventional hot melt adhesives lacking thermal stability easily phase-separate components in a high-temperature tank. Phase separation causes tank filters and transport piping to clog. In this respect, the point-adhesive composition of the present embodiment has good thermal stability and is uniformly melted in a high-temperature tank at 100 to 220 ° C, and phase separation is suppressed.

In the manufacturing line of disposable products for sanitary materials, hot melt adhesives are generally applied to various members of disposable products (e.g., tissues, cotton, nonwoven fabrics, polyolefin films, etc.). At the time of application, a hot melt adhesive can be ejected from various ejectors and used.

Hot melt point adhesives for disposable products for sanitary materials are suitable for spiral applications. The ability to apply a hot melt point adhesive to a wide width with a spray coat is very useful for making disposable products. The hot melt adhesive which can be applied in a wide width makes it possible to narrow the coating width by adjusting the pressure of the hot air.

If the hot melt point adhesive is difficult to apply in a wide width, a large number of spray nozzles are required to obtain a sufficient adhesive area, and it is also unsuitable for manufacturing a relatively small disposable product such as an adult pad or a disposable product having a complicated shape.

In this respect, the adhesive composition of the present embodiment is suitable for disposable products for sanitary materials, because it can be spirally coated with a wide width.

The pressure-sensitive adhesive composition of the present embodiment is excellent in the potting property at 150 캜 or less, and thus is useful for the production of disposable articles for sanitary materials. When the hot melt adhesive is applied at a high temperature, the appearance of the disposable product is significantly damaged because the polyolefin (preferably polyethylene) film as the base of the disposable product is melted or thermally contracted. When the hot melt point adhesive is applied at 150 DEG C or less, the appearance of the polyolefin (preferably polyethylene) film or the nonwoven fabric which is the base of the disposable product hardly changes and the appearance of the product is not damaged.

The pressure-sensitive adhesive composition of the present embodiment is excellent in high-speed coating applicability and is therefore suitable for producing a disposable product for sanitary materials in a short time. When a hot melt point adhesive is applied to a base material conveyed at a high speed, in a contact type coating method, breakage of the base material due to friction may occur. The pressure-sensitive adhesive composition of the present embodiment is suitable for spiral coating, which is one kind of non-contact coating, so that it is possible to improve production efficiency of high-speed coating and single use product. Further, the pressure-sensitive adhesive composition of the present embodiment suitable for high-speed coating does not break the coating pattern.

〔Usage〕

The pressure-sensitive adhesive composition of the present embodiment has good solubility, coatability, discharge stability, and surface texture, and is excellent in tackiness and adhesive force, and also has good balance of the sticking property. Taking advantage of these features, it can be applied to various adhesive tapes and labels, pressure-sensitive thin plates, pressure-sensitive sheets, surface protective sheet films, backs for fixing various lightweight plastic parts, backs for fixing carpets, backs for fixing tiles, adhesives And can be suitably used particularly for a point adhesive for various applications such as adhesive tape, adhesive sheet film, adhesive label, surface protective sheet film, and sanitary material.

Example

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, the properties and physical properties of the polymer were measured by the following methods.

[(1) Properties of Hydrogenated Block Copolymer Composition < (1-1) Weight average molecular weight >

Was measured by the following measuring method (1). However, when the molecular weight of the component (B) is 2.5 times or more the molecular weight of the component (A) when measured by the measurement method (1), the measurement is carried out by the measurement method (2) The weight average molecular weights of the component (A) and the component (B) were determined.

1. Measurement method (1)

The weight average molecular weights of the component (A) and the component (B) were measured using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene on the basis of measurement conditions described later, Hydrogenation) was determined based on the peak of the chromatogram obtained by using the block copolymer composition as a measurement sample. That is, the weight average molecular weight was determined using HLC-8320EcoSEC collection as measurement software and HLC-8320 analysis as analysis software.

Among the peaks having a peak top in the molecular weight range of 30,000 or more and having an area ratio of 0.1 or more with respect to the total peak area of the block copolymer composition as judged from the manufacturing method (polymerization method and type and amount of coupling agent) Wherein the peak of the top molecular weight is the peak of the component (A), the peak top molecular weight is higher than the molecular weight of the component (A), the peak top is in the range of the molecular weight of 50,000 or more, As a peak of the component (B).

Each weight average molecular weight of the component (A) and the component (B) is determined by the vertical division from the inflection points between the peaks of the GPC curve in the system and software described later to the base line. Here, the inflection point between the peaks was set as a lowest point (bone peak) in the most vertical direction between adjacent peaks. When the lowest point is continuous, the midpoint is set. Using the above-described inflection point, the waveform division function in the system / software described above was used to perform vertical division, and after division, the respective weight average molecular weights and area ratios were calculated.

(Measuring conditions)

GPC: HLC-8320GPC (manufactured by TOSOH CORPORATION)

System (measurement and analysis) software: HLC-8320EcoSEC collection, HLC-8320 analysis (made by Tosoh Corporation)

Detector: RI

Detection sensitivity: 3 ㎷ / min

Sampling pitch: 600msec

Column: 4 TSKgel superHZM-N (6 mm ID × 15 cm) (manufactured by Tosoh Corporation)

Solvent: THF (tetrahydrofuran)

Flow rate: 0.6 mm / min

Concentration: 0.5 mg / mL

Column temperature: 40 DEG C

Injection volume: 20 μL

2. Measurement method (2)

The weight average molecular weights of the component (A) and the component (B) were measured by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene on the basis of measurement conditions described later Hydrogenation) was determined based on the peak of the chromatogram obtained by using the block copolymer composition as a measurement sample. That is, the weight average molecular weight was determined using Empower 3 as measurement and analysis software. For hydrogenation, the molecular weight of the polymer after hydrogenation was measured.

First, a peak having a peak in the molecular weight range of 30,000 or more, and a peak area of the peak top molecular weight among the single peaks having an area ratio of 0.2 or more calculated by the peak division described below to the total peak area of the block copolymer composition The peak of the component (A) and the peak of a higher molecular weight range (however, the peak having a weight average molecular weight of less than 1,000,000) were defined as the component (B).

Each weight average molecular weight of the component (A) and the component (B) is determined by the vertical division from the inflection points between the peaks of the GPC curve in the system and software described later to the base line. Here, the inflection point between the peaks was set as a lowest point (bone peak) in the most vertical direction between adjacent peaks. When the lowest point is continuous, the midpoint is set. Using the above-described inflection point, the waveform division function in the system / software described above was used to perform vertical division, and after division, the respective weight average molecular weights and area ratios were calculated.

(Measuring conditions)

GPC: ACQUITY APC system (manufactured by Nihon Waters Co., Ltd.)

System (measurement and analysis) software; Empower 3 (manufactured by Nihon Waters Corporation) Detector: RI

Refractive Index Unit Full Scale: 500μRIU

Output Full scale: 2000㎷

Sampling rate: 10 points / sec

column: ACQUITY APC XT125 (4.6 mm x 150 mm); One

ACQUITY APC XT200 (4.6 mm x 150 mm); One

ACQUITY APC XT900 (4.6 mm x 150 mm); One

CQUITY APC XT450 (4.6 mm x 150 mm); One

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Concentration: 0.1 mg / mL

Column temperature: 40 DEG C

Injection volume: 20 μL

&Lt; (1-2) Content of Component (A) and Component (B) >

(A) and the peak area (B) of each of the components (A) and (B) determined by the method described in (1-1) with respect to the total peak area of the elution curve measured in the above- , The content of the component (A) and the component (B) was determined.

The area ratio was obtained by vertical division at the inflection point of each peak-to-peak curve using the analysis software HLC-8320 analysis.

<(1-3) Content of vinyl aromatic hydrocarbon monomer unit (styrene)>

An amount of the hydrogenated block copolymer composition was dissolved in chloroform and the absorption wavelength (262 nm (nm)) attributable to the vinyl aromatic hydrocarbon component (styrene) in the solution was measured using an ultraviolet spectrophotometer (UV-2450, Shimadzu Seisakusho Co., ) Was measured. From the peak intensity obtained, the content of the vinyl aromatic hydrocarbon monomer unit (styrene) was calculated using a calibration curve.

<(1-4) Conjugate Diene Compound The amount of vinyl bond in the monomer unit and the hydrogenation rate of the conjugated diene compound monomer unit>

The amount of vinyl bond in the hydrogenated block copolymer composition and the total hydrogenation rate of the unsaturated double bond based on the conjugated diene compound were measured by nuclear magnetic resonance spectrum analysis (NMR) under the following conditions.

A large amount of methanol was added to the reaction solution after the hydrogenation reaction, whereby the hydrogenated block copolymer composition was precipitated and recovered. Subsequently, the recovered hydrogenated block copolymer composition was extracted with acetone, and the hydrogenated block copolymer composition was vacuum dried. This was used as a sample for ¹ H-NMR measurement, and the total hydrogenation ratio and the amount of vinyl bond were measured.

The measurement conditions of ¹ H-NMR were as follows.

(Measuring conditions)

Measuring instrument: JNM-LA400 (made by JEOL)

Solvent: deuterated chloroform

Measurement sample: Before and after the hydrogenation of the polymer

Sample concentration: 50 mg / mL

Observation frequency: 400㎒

Chemical shift reference: TMS (tetramethylsilane)

Pulse delay: 2.904 seconds

Number of scans: 64

Pulse width: 45 °

Measuring temperature: 26 ° C

<(1-5) Maximum value of loss coefficient tan δ of dynamic viscoelastic spectrum>

The dynamic viscoelastic spectrum was measured by the following method to obtain the maximum value of the loss coefficient tan?.

First, the hydrogenated block copolymer composition was molded into a sheet having a thickness of 2 mm, and then cut into a size of 10 mm in width and 35 mm in length to obtain a sample for measurement.

The measurement sample was set in the twist type geometry of the device ARES (trade name, manufactured by TA Instruments Co., Ltd.), and the effective measurement length was 25 mm, the distortion was 0.5%, the frequency was 1 Hz, And the rate of temperature increase was 3 DEG C / min.

<(1-6) SP value>

The molar volume and moles of cohesive energy were determined according to the Bicerano method.

Further, when the SP value of a polymer block mainly composed of a conjugated diene compound is determined, it is preferable that the hydrogen-free 1,2-bond, the 1,2-bond after hydrogenation, the 1,4- The content of each component of the 1,4-bond was calculated from the hydrogenation rate and the amount of vinyl bond as follows.

1,2-bond (mol%) not added with hydrogen; (Amount of vinyl bond) - (1,2-bond after hydrogenation)

1,2-bond after hydrogenation (mol%); (Amount of vinyl bonding) x (amount of vinyl bonding)

1,4-bond (mol%) not added with hydrogen; 100 - (amount of vinyl bond) - (1,4-bond after hydrogenation)

1,4-bond (mol%) after hydrogenation; (Hydrogenation rate) - (1,2-bond after hydrogenation)

[(2): Measurement of physical properties of the pressure-sensitive adhesive composition]

(Production of a point-adhesive composition (compounding α, compounding β, compounding γ)

(A): 140 parts by mass (100 parts by mass for Example 16 and Example 20) of Quintone R100 (manufactured by Nippon Zeon Co., Ltd.), which is a tackifier, with respect to 100 parts by mass of the hydrogenated block copolymer composition, And 30 parts by mass of oil NS-90S (manufactured by Idemitsu Kosan Co., Ltd.) were blended and melt-kneaded at 180 占 폚 for 30 minutes with a pressurized double female kneader (type: D0.3-3, manufactured by Moriyama Seisakusho Co., Ltd.) To obtain a homogeneous hot melt type point adhesive composition.

180 parts by mass of Quintone R100 (manufactured by Nippon Zeon Co., Ltd.) as a tackifier and 100 parts by mass of Diana Process Oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) as a softener were added to 100 parts by mass of the hydrogenated block copolymer composition, And the mixture was melt-kneaded at 180 占 폚 for 30 minutes with a pressurized double-arm type kneader (type: D0.3-3, manufactured by Moriyama Seisakusho Co., Ltd.) to obtain a homogeneous hot-melt type point adhesive composition.

Formulation y: In the blend shown in Table 5, melt kneading was conducted at 180 占 폚 for 30 minutes with a pressurized double female kneader (type: D0.3-3, manufactured by Moriyama Seisakusho Co., Ltd.) to obtain a homogeneous hot melt type point- &Lt; / RTI &gt;

In each of the point adhesive compositions, 2 parts by weight of 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) Acrylate was added in an amount of 1 part by mass.

&Lt; (2-1-1) Melt viscosity of the pressure-sensitive adhesive composition (compound a)

The melt viscosity of the pressure-sensitive adhesive composition was measured by a Brookfield viscometer (DV-III manufactured by Brookfield) at a temperature of 180 ° C. Based on the obtained values, the melt viscosity was evaluated according to the following criteria. The evaluations were rated as?,?, And?

   Melting point (Pa 占 퐏)? 50 : ◎

50 < Melt viscosity (Pa? S)? 150 : ○

150 < melt viscosity (Pa s) : ×

&Lt; (2-1-2) Melt viscosity of the pressure-sensitive adhesive composition (formulation β)

The melt viscosity of the pressure-sensitive adhesive composition was measured by a Brookfield viscometer (DV-III, manufactured by Brookfield) at a temperature of 160 캜. Based on the obtained values, the melt viscosity was evaluated according to the following criteria. The evaluations were given as O, A, and X from the preferred order.

   Melting point (Pa 占))? 15 : ○

15 < Melt viscosity (Pa s)? 50 : △

50 < melt viscosity (Pa s) : ×

&Lt; (2-2-1) Intrusion of the viscous composition (compound a)

In order to evaluate the touch feeling of the pressure-sensitive adhesive composition, the length of entry of the prescribed needle into the pressure-sensitive adhesive composition maintained at 25 캜 in a constant-temperature water bath in accordance with JIS-K 2207 for 5 seconds was measured. The evaluations were rated as?,?,?, And?

   Intrusion (1 / 10mm) ≥60 : ◎

60> Intrusion (1 / 10mm) ≥45 : ○

45> Intrusion (1 / 10mm) ≥30 : △

30 > penetration (1/10 mm) : ×

&Lt; (2-2-2) Intrusion of viscous composition (compound beta, compound gamma)

In order to evaluate the touch feeling of the pressure-sensitive adhesive composition, the length of entry of the prescribed needle into the pressure-sensitive adhesive composition maintained at 25 캜 in a constant-temperature water bath in accordance with JIS-K 2207 for 5 seconds was measured. The evaluations were rated &quot; o &quot; and &quot; x &quot;

   Intrusion depth (1 / 10mm) ≥ 40 : ○

40> penetration (1/10 mm) : ×

(Production of adhesive tape)

The melted point-stick composition was cooled to room temperature and dissolved in toluene. The obtained toluene solution was coated on a PET film with an applicator, and then kept at room temperature for 30 minutes and at 70 DEG C for an oven for 7 minutes to completely evaporate toluene to prepare an adhesive tape. The thicknesses of the PET film and the pressure-sensitive adhesive layer as the base material of the adhesive tape were 50 탆 / 40 탆 in the case of the viscous composition (compound a) and 38 탆 / 30 탆 in the case of the viscose composition (compound 硫), respectively.

<(2-3) Probe tack of the point-adhesive composition (compounding α, compounding γ)>

The probe tack of the point-adhesive composition was measured according to ASTM D2979. The adhesive tape was attached to a weight (10 g load) at a temperature of 23 캜, and then the probe (5 mmφ) was brought into contact with the adhesive tape at a speed of 1 mm / sec. After 1 second, the probe was detached at a rate of 1 mm / sec. The maximum value at that time was measured as the value of the probe tag, and the tag was evaluated. The evaluations were rated as?,?,?, And?

    Probe tack (N / 5 mmφ) ≥ 2.0 : ◎

2.0> probe tag (N / 5 mm?)? 1.2 : ○

1.2> probe tag (N / 5 mm?)? 0.6 : △

0.6> probe tag (N / 5 mm?) : ×

&Lt; (2-4-1) Adhesive force of the pressure-sensitive adhesive composition (compound a) >

An adhesive tape having a width of 25 mm was attached to the SUS plate, and the adhesive tape was removed at a peeling speed of 300 mm / min, and the 180 peeling force at that time was measured. Based on the obtained peel force, the adhesive strength of the adhesive composition was evaluated according to the following criteria. The evaluations were given as O, A, and X from the preferred order.

7? Adhesive force (N / 10 mm) : ○

4? Adhesive force (N / 10 mm) <7 : △

   Adhesive force (N / 10 mm) < 4 : ×

&Lt; (2-4-2) Adhesive force of the pressure-sensitive adhesive composition (compounding?, Compounding?)>

An adhesive tape having a width of 25 mm was attached to the SUS plate, and the adhesive tape was removed at a peeling speed of 300 mm / min, and the 180 peeling force at that time was measured. Based on the obtained peel force, the adhesive strength of the adhesive composition was evaluated according to the following criteria. The evaluations were rated &quot; o &quot; and &quot; x &quot;

5? Adhesive force (N / 10 mm) : ○

   Adhesive force (N / 10 mm) < 5 : ×

<Retention of (2-5-1) point adhesive composition (compound a)>

An adhesive tape was attached to the SUS plate so that an area of 15 mm x 15 mm was in contact with the tape. A load of 1 kg was applied at 50 캜 to measure the time until the adhesive tape fell off. Based on the obtained time, the holding power of the pressure-sensitive adhesive composition was evaluated according to the following criteria. The evaluations were rated as?,?,?, And?

300? Retention force (minute) : ◎

130? Retention force (minute) < 300 : ○

Holding force (min) < 130 : △

    Retention force (min) <70 : ×

<Retention of (2-5-2) point adhesive composition (compounding β, compounding γ)>

An adhesive tape was attached to an SUS plate so that an area of 25 mm x 15 mm was in contact with the tape. A load of 1 kg was applied at 50 캜 to measure the time until the adhesive tape fell off. Based on the obtained time, the holding power of the pressure-sensitive adhesive composition was evaluated according to the following criteria. The evaluations were given as O, A, and X from the preferred order.

Retention force (min) : ○

5? Holding force (minute) < 30 : △

   Retention force (min) <5 : ×

&Lt; (2-6) Ball tack of the point adhesive composition (compound beta) >

The tack of the pressure-sensitive adhesive composition obtained in Examples and Comparative Examples was evaluated by an inclined ball tack in accordance with JIS-Z0237. Specifically, a triangular device (having an inclination angle of 30 degrees) having a starting point for putting a steel ball, an auxiliary path (100 mm) leading to the starting point, and an adhesive surface (100 mm) ) Was prepared, and a steel ball (size: 1/32 to 32/32 inch) was rolled from the base point above the inclined surface toward the adhesion surface below the inclined surface. The numerical value of 32 times the ball size stopped on the adhesive surface was called &quot; ball number &quot;, and the maximum ball number stopped on each adhesive tape was measured. On the basis of the obtained ball number, the tack of the pressure-sensitive adhesive composition was evaluated according to the following criteria. The evaluations are given as?,?, X from the good order.

25 &lt; : ○

20 &amp;bull; &lt; 25 : △

    Ball number <20 : ×

[(3): Preparation of hydrogenation catalyst]

In the following Examples and Comparative Examples, the hydrogenation catalyst used in preparing the hydrogenated block copolymer composition was prepared by the following method. The reaction vessel equipped with the stirrer was purged with nitrogen, to which 1 L of cyclohexane dried and purified was added. Then, 100 mmol of bis (? 5-cyclopentadienyl) titanium dichloride was added. With sufficient stirring, an n-hexane solution containing 200 mmol of trimethylaluminum was further added and the mixture was reacted at room temperature for about 3 days. Thus, a hydrogenation catalyst was obtained.

[(4): Preparation of hydrogenated block copolymer composition]

&Lt; Preparation Example 1 &

A stainless steel autoclave having an inner volume of 40 L equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and 5960 g of cyclohexane was charged. Hot water was passed through the jacket to set the content at 70 캜. 2.5 g of N, N, N ', N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) and a solution of n-butyllithium cyclohexane (3.79 g as pure water) were added and a cyclohexane solution Gt; 430g) &lt; / RTI &gt; was added sequentially. The polymerization conversion rate of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (2600 g in terms of pure water) was continuously added to continue the polymerization. The polymerization conversion rate of butadiene was 100%. Thereafter, 4.84 g of a coupling agent was added to conduct a coupling reaction. As the coupling agent, Epototo ZX-1059 (Shin Nitetsu Sumikin Kagaku K.K.) and cyclohexane were mixed at a mass ratio of 90:10. After the addition of the coupling agent, 0.70 g of methanol was added for inactivation. The monomer was always added at three points while being controlled so as to be added to the polymerization solution. The temperature difference between the point of time when the temperature of the solution under polymerization and the point of maximum temperature was 3.2 ° C.

The hydrogenation catalyst prepared as described above was added to the obtained block copolymer composition solution in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer composition, and the hydrogenation reaction was carried out in the continuous process. The ratio of the height (H) to the inner diameter (D) of the reactor (H / D) of the reactor used was 5.2 and the difference between the maximum and minimum values of the solution temperature during the hydrogenation was 3.2 ° C. The total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 52 mol%.

To the obtained hydrogenated block copolymer composition solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added in an amount of 0.3 part by mass relative to 100 parts by mass of the block copolymer composition And the mixture was thoroughly mixed. Thereafter, the solvent was removed by heating to obtain the composition of Production Example 1. The resulting hydrogenated block copolymer composition had a styrene content of 14 mass% and an average vinyl bond amount of butadiene part of 38 mass%. The content of the component (A) in the obtained hydrogenated block copolymer composition was 48 mass%, the weight average molecular weight was 115,000, the content of the component (B) was 52 mass%, and the weight average molecular weight was 228,000. The molecular weight and content were determined according to the measurement method (1). The maximum value of tan δ was 1.5.

&Lt; Preparation Example 2 &

(Component (A))

A stainless steel autoclave having an inner volume of 40 L equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen. Cyclohexane was added thereto, and hot water was passed through the jacket to set the content at 65 캜. TMEDA and n-butyllithium cyclohexane solution were added, and a cyclohexane solution containing styrene was added continuously. The polymerization conversion rate of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene was continuously added to continue the polymerization. The polymerization conversion rate of butadiene was 100%. After that, methanol was added to inactivate. The monomer was always added from three places while being controlled so as to be added to the polymerization solution. The temperature difference between the point of time when the temperature of the solution under polymerization and the point of maximum temperature was 3.8 ° C.

The hydrogenation catalyst prepared as described above was added to the obtained block copolymer solution in an amount of 100 ppm based on Ti based on 100 parts by mass of the block copolymer and hydrogenated at a hydrogen pressure of 0.8 MPa and an average temperature of 110 캜 in a continuous process . The H / D ratio of the used hydrogenation reactor was 5.2, and the difference between the maximum value and the minimum value of the solution temperature during the hydrogenation reaction was 4.2 ° C.

To the obtained hydrogenated block copolymer solution, 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate relative to 100 parts by mass of the block copolymer was added , And sufficiently mixed. By the above operation, the component (A) of Production Example 2 was obtained.

(Component (B))

A stainless steel autoclave having an inner volume of 40 L equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen. Cyclohexane was added thereto, and hot water was passed through the jacket to set the content at 65 캜. TMEDA and n-butyllithium cyclohexane solution were added, and a cyclohexane solution containing styrene was added continuously. The polymerization conversion rate of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene was continuously added to continue the polymerization. The polymerization conversion rate of butadiene was 100%. Subsequently, a cyclohexane solution containing styrene was continuously added to continue the polymerization. The polymerization conversion rate of styrene was 100%. After that, methanol was added to inactivate. The monomer was always added from three places while being controlled so as to be added to the polymerization solution. The temperature difference between the point of time when the temperature of the solution under polymerization and the point of maximum temperature was 3.8 ° C.

The hydrogenation catalyst prepared as described above was added to the obtained block copolymer solution in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer and hydrogenated at a hydrogen pressure of 0.8 MPa and an average temperature of 110 占 폚 in a continuous process . The H / D ratio of the used hydrogenation reactor was 5.2, and the difference between the maximum value and the minimum value of the solution temperature during the hydrogenation reaction was 4.1 ° C.

To the obtained hydrogenated block copolymer solution, 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate relative to 100 parts by mass of the block copolymer was added , And sufficiently mixed. By the above operation, the component (B) of Production Example 2 was obtained.

Finally, the hydrogenated block copolymer solution containing the component (A) and the hydrogenated block copolymer solution containing the component (B) were mixed and the solvent was removed by heating to obtain the hydrogenated block copolymer of Production Example 2 A composition was obtained. A part of the obtained reaction solution was taken out, and the same measurement as in Production Example 1 was carried out. The measured values are shown in Table 1.

&Lt; Production Examples 3 to 18, 22 and 23 >

Except that the amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, coupling agent and methanol, and the production conditions were changed as shown in Table 1, respectively. 22, and 23, respectively. For these hydrogenated block copolymer compositions, the same measurements as in Production Example 1 were carried out. The results are shown in Table 1.

&Lt; Preparation Examples 19 to 21 &

Except that the amount of TMEDA, n-butyllithium, styrene, 1,3-butadiene, the amount of coupling agent and methanol, the kind of coupling agent, and the production conditions were changed as shown in Table 1, The hydrogenated block copolymer compositions of Examples 19 to 21 were obtained. Further, tetraethoxysilane was used as a coupling agent. These hydrogenated block copolymer compositions were subjected to the same measurement as in Production Example 1 except for the measurement of the molecular weight and the content. The molecular weight and content were determined according to the measurement method (2). The results are shown in Table 1.

&Lt; Example 1 >

Using the hydrogenated block copolymer composition of Production Example 1, a homogeneous hot-melt type point adhesive composition was obtained by the above-mentioned production method of the pressure-sensitive adhesive composition (formulation a). Further, the pressure-sensitive adhesive tape was obtained by the above-mentioned method of producing the pressure-sensitive adhesive tape. The physical properties of the above-mentioned pressure-sensitive adhesive compositions were measured using these pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes. The results are shown in Table 2.

&Lt; Examples 2 to 13 and Comparative Examples 1 to 7 >

The procedure of Example 1 was repeated except that the hydrogenated block copolymer compositions of Production Examples 2 to 11, 18, 19, 12 to 17, and 23 were used in place of the hydrogenated block copolymer composition of Production Example 1, The adhesive composition and the adhesive tape were respectively prepared and the properties were evaluated. The results are shown in Table 2. Further, when the torque was not stabilized even after 30 minutes of kneading, the kneading was continued until the torque became stable.

&Lt; Examples 14, 15, 17 to 19 >

The procedure of Example 1 was repeated except that 100 parts by mass of the hydrogenated block copolymer composition of Example 1 was used instead of 100 parts by mass of the polymer composition mixed with the polymer blend examples 1 to 5 shown in Table 4, An adhesive composition and an adhesive tape were prepared. Table 2 shows the evaluation results of each of the resulting point adhesive compositions and adhesive tapes.

&Lt; Example 16 >

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape were prepared in the same manner as in Example 1, except that 100 parts by mass of the same tackifier was used instead of 140 parts by mass of the tackifier of Example 1. Table 2 shows the evaluation results of each of the resulting point adhesive compositions and adhesive tapes.

&Lt; Example 20 >

Except that the hydrogenated block copolymer composition of Production Example 19 was used in place of the hydrogenated block copolymer composition of Production Example 1 and 100 parts by mass of the same tackifier was used instead of 140 parts by mass of the tackifier. 1, a point-adhesive composition and a pressure-sensitive adhesive tape were respectively prepared. Table 2 shows the evaluation results of each of the resulting point adhesive compositions and adhesive tapes.

&Lt; Example 21 >

Using the hydrogenated block copolymer composition of Production Example 1, a homogeneous hot melt type point adhesive composition was obtained by the above-mentioned production method of the pressure-sensitive adhesive composition (compounding?). Further, the pressure-sensitive adhesive tape was obtained by the above-mentioned method of producing the pressure-sensitive adhesive tape. The physical properties of the above-mentioned pressure-sensitive adhesive compositions were measured using these pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes. The results are shown in Table 3.

&Lt; Examples 22 to 26 and Comparative Example 8 >

The procedure of Example 21 was repeated except that the hydrogenated block copolymer compositions of Production Examples 4, 6, 19 to 21 and 23 were used in place of the hydrogenated block copolymer composition of Production Example 1 to obtain a pressure- Each of the tapes was produced, and the characteristics were evaluated. The results are shown in Table 3. Further, when the torque was not stabilized even after 30 minutes of kneading, the kneading was continued until the torque became stable.

&Lt; Examples 27 to 31 >

The procedure of Example 1 was repeated except that 100 parts by mass of the hydrogenated block copolymer composition of Example 21 was used instead of 100 parts by mass of the polymer composition mixed with the polymer blend examples 6 to 10 shown in Table 4, An adhesive composition and an adhesive tape were prepared. Table 3 shows the evaluation results of each of the resulting point adhesive compositions and adhesive tapes.

&Lt; Examples 32 to 35 >

A homogeneous hot-melt type point adhesive composition was obtained by the above-mentioned method of preparing the pressure-sensitive adhesive composition (formulation γ) so as to obtain the compositions of Formulation Examples 11 to 14 shown in Table 4. Further, the pressure-sensitive adhesive tape was obtained by the above-mentioned method of producing the pressure-sensitive adhesive tape. The physical properties of the above-mentioned pressure-sensitive adhesive compositions were measured using these pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes. The results are shown in Table 5.

The structures of the components (A) and (B) in Table 1 are structures estimated from the production method.

The numerical values in Table 4 indicate the number of mass parts. Each component in the table is as follows. Further, all of the following (P1) to (P3) are not hydrogenated.

(P1) non-hydrogenated styrene-isoprene block copolymer (hydrogenation rate: 0%)

(P1-1) D1161 (manufactured by Kraton Polymer)

SI / SIS, a styrene content of 16% by mass, an SI content of 20%

(P1-2) Quintax 3433N (manufactured by Nippon Zeon Co., Ltd.)

SI / SIS, styrene content 15 mass%, SI content 78 mass%

(P1-3) Quintax 3460 (manufactured by Nippon Zeon Co., Ltd.)

SI / (SI) ₃ X, a styrene content of 25 mass%, an SI content of 30 mass%

In the above formula, "S" represents a styrene block, "I" represents an isoprene block, and "X" represents a coupling agent residue.

(P2) non-hydrogenated styrene-butadiene block copolymer (hydrogenation rate: 0%)

(P2-1) D1102 (manufactured by Kraton Polymer)

(P3) modified styrene-butadiene block copolymer

(P3-1) Toughprene T912 (manufactured by Asahi Kasei Chemicals Co., Ltd.)

In the above formula, "S" represents a styrene block and "B" represents a butadiene block.

(T) Tackifier

(T1) Hydrogenated petroleum resin Alcon P100 (manufactured by Arakawa Chemical Industries, Ltd.)

(T2) hydrogenated petroleum resin Alcon M100 (manufactured by Arakawa Chemical Industries, Ltd.)

(T3) Rosin ester resin Super ester A100 (manufactured by Arakawa Chemical Industries, Ltd.)

(O) Oils

(O1) paraffin oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.)

INDUSTRIAL APPLICABILITY The pressure-sensitive adhesive composition of the present invention can be applied to various types of pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive sheets, adhesive labels, pressure-sensitive thin plates, pressure- It can be used for adhesive tape, adhesive tape, adhesive film, adhesive label, surface protective sheet, surface protective film, sanitary material point It is industrially applicable as an adhesive.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2014-103809) filed on May 19, 2014 with the Japanese Patent Office, the contents of which are incorporated herein by reference.

Claims (19)

(A) containing a polymer block composed mainly of at least one vinyl aromatic hydrocarbon and a polymer block composed mainly of at least one conjugated diene compound and having a weight average molecular weight of 30,000 or more and 500,000 or less,
(B) containing a polymer block composed mainly of at least two vinyl aromatic hydrocarbons and a polymer block composed mainly of at least one conjugated diene compound and having a weight average molecular weight of 50,000 or more and 1,000,000 or less,
Lt; / RTI &gt;
A hydrogenated block copolymer composition which satisfies the following requirements (a) to (c):
(a) the total hydrogenation ratio H (%) of the unsaturated double bond based on the conjugated diene compound is 5 to 90%
(b) the maximum value of the loss coefficient tan? at -100 DEG C to 0 DEG C is 0.4 to 4.0
(c) a ratio of the weight average molecular weight of the component (A) to the component (B)
(Weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3 to 10. The hydrogenated block copolymer composition according to claim 1, wherein the component (A) is 20 mass% or more and 90 mass% or less, and the component (B) is 10 mass% or more and 80 mass% or less. The hydrogenated block copolymer composition according to claim 1 or 2, wherein the SP value is 17.2 (MPa) ^1/2 or more and 17.7 (MPa) ^1/2 or less. Claim 1 to claim 3, wherein according to any one of, wherein the conjugated diene compound polymer block is an SP value of 16.8 (㎫) ^1/2 or more of a subject, not more than 17.5 (㎫) ^1/2, the hydrogenated block copolymer Lt; / RTI &gt; The hydrogenated block copolymer composition according to any one of claims 1 to 4, wherein the component (B) has a weight average molecular weight of 140,000 or more and 600,000 or less. The positive resist composition according to any one of claims 1 to 5, wherein the component (B) is at least one compound selected from the group consisting of a polymer block composed mainly of two vinyl aromatic hydrocarbons and a polymer block composed mainly of at least one conjugated diene compound. Additive block copolymer composition. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the component (B) has a weight average molecular weight of 200,000 or more and 600,000 or less. The hydrogenated block copolymer composition according to any one of claims 1 to 7, wherein the conjugated diene compound is butadiene. The hydrogenated block copolymer composition according to any one of claims 1 to 8, wherein the content of the vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer composition is from 5 mass% to less than 35 mass%. 10. The hydrogenated block copolymer composition according to any one of claims 1 to 9, wherein the content of the vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer composition is 5 mass% or more and less than 20 mass%. 11. The hydrogenated block copolymer composition according to any one of claims 1 to 10, wherein the maximum value of the loss coefficient tan is 0.7 to 1.6. 12. The hydrogenated block copolymer composition according to any one of claims 1 to 11, wherein the maximum value of the loss coefficient tan delta is 0.9 to 1.6. 13. The hydrogenated block copolymer composition according to any one of claims 1 to 12, wherein the temperature at which the maximum value of the loss coefficient tan? Is taken is not lower than -75 占 폚 and not higher than -50 占 폚. 14. The hydrogenated block copolymer composition according to any one of claims 1 to 13, wherein the component (A) has a weight average molecular weight of 70,000 or more and 300,000 or less. A pressure-sensitive adhesive composition comprising the hydrogenated block copolymer composition according to any one of claims 1 to 14,
With respect to 100 parts by mass in total of the polymer contained in the point adhesive composition,
20 to 500 parts by mass of the tackifier,
0 to 300 parts by mass of a softener
Wherein the pressure-sensitive adhesive composition further comprises a pressure-sensitive adhesive. 16. The point adhesive composition according to claim 15, further comprising a vinyl aromatic elastomer. The method according to claim 16, wherein the vinyl aromatic elastomer contains a polymer block composed mainly of at least one vinyl aromatic hydrocarbon and a polymer block composed mainly of at least one conjugated diene compound, Wherein the maximum value of the loss coefficient tan? In the conjugated diene compound is less than 0.4, and the hydrogenation ratio H (%) of the unsaturated double bond based on the conjugated diene compound is 5 to 90%. 18. The point-adhesive composition according to any one of claims 15 to 17, further comprising a conjugated diene-based synthetic rubber. 19. The point-adhesive composition according to any one of claims 15 to 18, further comprising a natural rubber.